WO2010037463A1 - Titanium dioxide particles - Google Patents

Abstract

The present invention relates to hydrothermally treated titanium dioxide particles, aftertreated with a silicon dioxide coating, the amount of SiO2 in the coating being 25 to 45 per cent by weight, based on the particles, and also to the preparation and use thereof.

Description

 Titanium dioxide particles

The present invention relates to titanium dioxide particles, their preparation and

Use.

The present invention further relates to novel preparations for topical

Application, in particular the self-tanning agent dihydroxyacetone in

Combination with the titanium dioxide particles of the invention to protect the

Skin and / or hair against UV radiation include.

Dihydroxyacetone (DHA) has been used as a self-tanning agent in cosmetics for many years. In recent years, the trend is also increasingly to combine self-tanning products with UV filters, for example, for day care. However, this has only been possible to a limited extent in the past, since DHA in combination with conventional inorganic UV filters, in particular TiO ₂ , shows a strong degradation during storage.

Conventional micronized titanium dioxide particles are aftertreated to reduce the photocatalytic activity with inorganic oxides or hydroxides of the elements Al, Si, Zr, Ce and Fe. Particularly suitable here is the aftertreatment with Al ₂ O ₃ . In addition to the photo-catalytic activity, which leads to the degradation or destruction of the surrounding matrix when these products are used, further undesirable effects occur, in particular in cosmetic formulations:

Degradation of DHA when combined in formulations with TiO ₂

Color reactions of the TiO ₂ particles with DHA and with other organic

Molecules in the preparation

Graying the formulations under UV irradiation.

Some of these effects, for example graying or color reactions with, for example, ascorbyl palmitate, can be reduced by various post-treatments of the titanium dioxide particles, for example achieved by the qualities of the market products Parsol® TX from DSM or UV-TITAN M263 from Kemira.

Parsol® TX is a white powder consisting of titanium dioxide of rutile crystal structure with a TiO ₂ content of 82.0 to 87.0 weight percent, with an SiO ₂ coating with an SiO ₂ content of 10.5 to 14.5 percent by weight and a dimethicone coating.

UV-TITAN M263 is a white powder consisting of titanium dioxide (88%) with an inorganic component of 7% aluminum phosphate and an organic component of 3% of polyvinylpyrrolidone (INCI of the product: Titanium Dioxide, Alumina, Sodium Hexametaphosphate, Polyvinylpyrrolidone).

However, it has been found that even known conventional micronized titanium dioxide particles, as described above, which are provided with various post-treatments such as SiO ₂ and / or further aftertreatments, and these show good photocatalytic stability and / or low reactivities with other organic molecules, do not automatically compatible with dihydroxyacetone.

The object of the invention is therefore to provide titanium dioxide particles as UV protectants which are compatible with dihydroxyacetone or dihydroxyacetone derivatives, in particular with dihydroxyacetone.

It has now surprisingly been found that it is possible to use certain titanium dioxide particles as UV protectants in cosmetic formulations containing dihydroxyacetone and thereby reduce or reduce the degradation of the dihydroxyacetone in the cosmetic formulations in comparison to known titanium dioxide UV protectants prevent. Furthermore, it has been found that these particular titanium dioxide particles also have the property of largely preventing color reactions of titanium dioxide with organic compounds, the photocatalytic activity and the graying stability remaining comparable to known titanium dioxide UV protection agents.

The object is achieved by the coating of hydrothermally treated titanium dioxide particles with a SiO ₂ coating, wherein the content of SiO ₂ in the range of 25 to 45 weight percent, in particular 33 to 37 weight percent, most preferably 35 weight percent, based on the TiO ₂ content of the particles to be coated. It was not foreseeable for a person skilled in the art that when focusing on a SiO ₂ content in the given ranges, the interaction of the titanium dioxide particles with dihydroxyacetone is so would be greatly reduced. Further after-treatment with organic acids selected from the group consisting of stearic acid, lauric acid, caproic acid or palmitic acid, with polyols or with organosilicon compounds may likewise be advantageous.

A first subject of the present invention are therefore hydrothermally treated titanium dioxide particles, aftertreated with a silicon dioxide coating, wherein the content of SiO ₂ in the coating 25 to 45 weight percent, based on the TiO ₂ content of the particles to be coated. In particular, the content of SiO _{2 is} 33 to 37 percent by weight, very particularly preferably 35 percent by weight, based on the TiO ₂ content of the particles to be coated.

The product obtained is characterized by a water content of> 1, 5Gew .-%. The water content can be determined, for example, by Karl Fischer titration, as described in Eugen Scholz, Karl Fischer Titration, Springer-Verlag 1984.

The determination of the content of SiO ₂ is based on ICP-OES. The fluctuation range of the obtained values of the content of SiO ₂ is in the specified range of 25 to 45% by weight based on the titanium dioxide at plus / minus 0.25%.

ICP-OES stands for Inductively Coupled Plasma Optical Emission Spectrometry, ie inductively coupled plasma optical emission spectrometry. It is measured with the Optima 3300DV device from Perkin Elmer, using the method described in the experimental part of the description under the example SiO ₂ determination.

The silicon dioxide coating should cover the titanium dioxide particles or, in other words, the particulate titanium dioxide, in particular the nanoparticulate titanium dioxide, as completely as possible.

The described titanium dioxide particles have a primary particle size according to the Scherrer method in the range of 5 nm to 100 nm, preferably in the range 8 to 50 nm and particularly preferably below 25 nm. The dimensions determinable in the transmission electron microscope of the nanoparticulate titanium dioxide according to the invention are usually one Length of 10 to 100 nm and a width of 5 to 70 nm. Preferably, the length is in the range of 30 to 70 nm and the width in the range of 10 to 40 nm.

Nanoparticles in the sense of the invention are particles whose three dimensions are present in the nanoscale, i. <100 nm. These are the three dimensions of the primary particles.

Aggregates in the sense of the invention are a combination of primary particles, by chemical or physical bonding, wherein the external surface is significantly smaller than the sum of the calculated surfaces of the individual particles, i. the primary particle. Aggregates according to the invention have dimensions of 30 nm to 150 nm.

Agglomerates within the meaning of the invention are a combination of primary particles or / and aggregates, by chemical or physical bonding, wherein the external surface is not significantly smaller than the sum of the calculated surfaces of the individual particles, but the dimensions in ranges between 0.1 microns and 100 microns are.

The term titanium dioxide particle therefore includes both the primary particles, as well as aggregates or agglomerates. In the course of a grinding, the size of the mergers of the primary particles can be adjusted to the desired size for use in the respective application.

A method for producing the titanium dioxide particles according to the invention is characterized, for example, by a) treating titanium dioxide particles, ie so-called titanium dioxide base particles, hydrothermally, b) subsequently applying a silicon dioxide coating in such a way that the content of SiO ₂ in the coating 25 to 45 percent by weight based on the TiO ₂ content of the particles to be coated and c) the suspension is dried.

As a hydrothermal treatment, the heating of an aqueous solution, or suspension or dispersion in a closed container, optionally under pressure, referred to (see also Ulimann's Encyclopedia of Technical Chemistry, 4th Edition, 1978, Volume 15, p.117 ff: K. Recker, single crystal growth).

The hydrothermal treatment of the titanium dioxide base particles is preferably carried out at temperatures in the range 40-360 ⁰ C, preferably in the range from 80 to 220 ⁰ C and most preferably in the range of 140 to 200 ° C.

The hydrothermal treatment leads to the formation of stable nano-crystallites of uniform size and shape. Crystallites form at low temperatures, crystallites round off as the temperature increases, forming oval foms that can grow to round particles at very high temperatures, and in addition to uniform crystal growth.

Advantages of the hydrothermal treatment over a conventional thermal treatment (temperature treatment of a dried powder) are:

Formation of uniform crystallite sizes with narrow particle size distribution - Prevention of sintering effects (formation of undesired

Aggregates).

Titanium dioxide can be present in the form of rutile or anatase or in amorphous form, but preferably in the form of rutile and / or anatase. Preferred primary particle sizes of the titanium dioxide base particles are in the range from 5 to 50 nm, whereby these primary particles are preferably round, in particular in anatase, while rutile primary particles frequently occur in needle or spindle form as far as ovals ("egg-shaped") also round rutile primary particles are used.

Titanium dioxide base particles can be prepared by wet-chemical methods according to conventional methods which are familiar to the person skilled in the art.

The silicon dioxide coating in step b) can preferably be carried out as a sol-gel process, with a water-glass solution being particularly preferably added to a suspension of the titanium dioxide.

In this case, the sol-gel process is carried out in an advantageous variant at a constant pH. The constant pH can be in a range of pH 2 to pH 11, wherein the pH is preferably in the range of pH = 5 to pH = 8, particularly preferably in the range of pH = 6 to pH = 7.

A further advantageous variant is the total addition of the water glass necessary for the aftertreatment at a pH = 7 to pH = 11 without pH constant maintenance. Subsequently, the pH is lowered to a value of pH = 5 to pH = 8, preferably to pH = 6 to pH = 7.

Further, it is preferred that step b) is carried out at elevated temperature, preferably at a temperature in the range of 50 ⁰ C to 11O ⁰ C.

In all the variants of the specified method, a maturing time after completion of the coating is advantageous. The ripening time should be between 1 h and 8 h, preferably 2 h to 4 h and carried out at a temperature of 50 ⁰ C to 110 ⁰ C.

The suspension obtained from b) can be used directly for the preparation of preparations comprising the titanium dioxide particles according to the invention. However, the suspension can also be dried.

Further, it may be advantageous in terms of later processing if the product is subsequently ground. Here, the usual milling techniques that can be used with nanoparticles can be used.

The nanoparticulate titanium dioxide according to the invention likewise has the advantageous properties of the comparison products from the prior art with regard to:

UV absorption, in particular broadband or UV-B absorption, transparency in visible light (VIS), good, in particular increased photostability, reduced or prevented photoactivity,

- Silica surface, which may be slightly hydrophobic, can be hydrophobically modified by known techniques, easy dispersibility in aqueous and oily phases,

in combination with dibenzoylmethane derivatives, in particular: o reduced discoloration of the formulation and / or diminishing discoloration of the formulation during

Storage and / or o no or reduced crystallization of complexes of

Dibenzoylmethane derivatives and / or o increased storage stability of the dibenzoylmethane derivatives and / or o improved light protection, especially after storage, - in combination with benzophenone derivatives, in particular 2-hydroxy-4-methoxy-benzophenone, a stabilization of the benzophenone derivatives observed.

However, the nanoparticulate titanium dioxide according to the invention according to claim 1 now shows in combination with dihydoxyacetone significantly reduced degradation of DHA after storage compared to conventional, previously known, titanium dioxide UV protection agents, ie it is compared to the prior art reduced significant destabilization of the self-tanner observed. It is therefore referred to as DHA compatible for the purposes of this invention. Furthermore, it has been shown that in combination with DHA no or only minimal discoloration of the preparation after preparation and after 3 months storage at 40 ⁰ C occurs.

It has been found, in particular, that it can be advantageous for the simultaneous realization of the abovementioned advantages if the nanoparticulate titanium dioxide is doped with iron.

In a further embodiment of the invention, the nanoparticulate titanium dioxide, as described above, can be further modified by applying, in addition to the SiO ₂ coating, a further coating containing organic acids selected from the group of stearic acid, lauric acid, caproic acid or palmitic acid, polyols or organosilicon compounds.

Examples of polyols are glycerol, sorbitol, propylene glycol, pentanediol,

Hexanediol, ethylhexyl glycerol, pentaerythritol, dipentaerythritol or

Trimethylolpropane.

Silicone organic compounds are, for example, silicone oils, also referred to below as silicones, or alkyl silanes. The silicones are known to be organosilicon polymers or oligomers having a straight-chain or cyclic, branched or crosslinked structure with different molecular weights, which are obtained by polymerization and / or polycondensation of suitably functionalized silanes and are formed essentially from repeating main units in which the silicon atoms are bonded via oxygen atoms linked together (siloxane bond), wherein optionally substituted hydrocarbon groups are bonded via a carbon atom directly to the silicon atoms. The most typical hydrocarbon groups are the alkyl groups and in particular methyl, the fluoroalkyl groups, the aryl groups and especially phenyl and the alkenyl groups and in particular vinyl. Further types of groups which can be attached to the siloxane chain either directly or via a hydrocarbon group are in particular hydrogen, the halogens and in particular chlorine, bromine or fluorine, the thiols, the alkoxy groups, the polyoxyalkylene groups (or polyethers) and in particular polyoxyethylene and / or polyoxypropylene, hydroxy groups or hydroxyalkyl groups, the optionally substituted amino groups, the amide groups, the acyloxy groups or acyloxyalkyl groups, the hydroxyalkylamino groups or aminoalkyl groups, quaternary ammonium groups, amphoteric groups or betaine groups, anionic groups such as carboxylates, thioglycolates, sulfosuccinates, thiosulfates, phosphates and sulfates Of course, this list is in no way limiting (so-called organomodified 'silicones).

The organosilicon compounds suitable for the present invention for coating the nanoparticulate titanium dioxide coated with SiO ₂ as described above are preferably selected from alkylsilanes or silicone oils, for example octyltrimethylsilane, methicone, dimethicone or simethicone. Very particular preference is aftertreatment with simethicone. The outer coating is at least 0.25 weight percent of the compound used for the outer secondary coating, preferably from 0.5 wt .-% to 50 wt .-%, particularly preferably from 0.5 wt .-% to 15 wt .-%, based on the TiO ₂ Content of the particles to be coated. The additional post-treatment enhances the already described advantages of the particles according to the invention, in particular the DHA compatibility.

Further preferred combinations of embodiments are disclosed in the claims.

Due to the above-mentioned advantages, a further subject of the present invention is a preparation comprising the titanium dioxide particles according to the invention, as described above.

For the purposes of the present invention, the term agent or formulation is used synonymously in addition to the term preparation.

Any compounds or components which may be used in the compositions are either known and commercially available or may be synthesized by known methods.

The preparations in a variant of the invention are aqueous or oily dispersions. Preferred oils are, for example, natural oils, such as sunflower oil; or the oils known for use in cosmetics, such as isononyl isononanoate; Isopropyl palmitate, propylheptyl caprylate; Dicaprylyl carbonate, butylene glycol dicaprylate / dicaprate, isopropyl lauroyl sarcosinate, C12-15 alkyl benzoate (for example Tegosoft TN from Evonik), capric / caprylic triglyceride, cyclopentasiloxane or cyclohexasiloxane.

The preparations in a variant of the invention are preferably topically applicable preparations, for example cosmetic or dermatological formulations. The preparations in this case contain a cosmetically or dermatologically suitable carrier and, depending on the desired property profile, optionally further suitable ingredients.

Further preferred preparations according to the invention are selected from the group fibers, textiles, including their coatings, paints, coating systems, films and packaging for the protection of food, plants or technical goods. The nanoparticulate titanium dioxide according to the invention, as described above, can be used for incorporation into paints, coating systems, films, packaging, fibers, textiles and molded parts made of rubber or silicone rubber, such as tires or insulators.

In addition to the advantages already mentioned above, the use of the titanium dioxide particles according to the invention in preparations which are emulsions can also contribute in particular to the stabilization of the emulsion. As a result, the use of emulsifiers can generally be reduced or, in individual cases (Pickering emulsion), even completely dispensed with the use of emulsifiers. Emulsifier-free emulsions which contain the nanoparticulate titanium dioxide according to the invention are therefore also preferred according to the invention.

The titanium dioxide particles according to the invention can be present in the inventive compositions in proportions which are generally in the range from 0.1% by weight to 50% by weight and preferably in proportions which are in the range of 0.5% by weight. to 20 wt .-%, these proportions are based on the total weight of the preparation.

Preferred formulations include dihydroxyacetone or a

Dihydroxyacetone derivative, most preferably dihydroxyacetone. HX-OH

I

C = O

I

H ₂ C-OH 1, 3-dihydroxyacetone (DHA)

The concentration of DHA in the preparation is in the range from 1 to 12 percent by weight, preferably from 1.5 percent by weight to 7.5 percent by weight, more preferably from 2 percent by weight to 5 percent by weight, based on the preparation.

These formulations are characterized in that the degradation of the DHA after storage for 3 months at 4O ⁰ C in the dark at a use ratio of TiO ₂ according to the invention: DHA (wt .-%) of a) <= 0.5: 1

-> is not greater than max. 50% (preferably 25%) in terms of DHA degradation in the same formulation without the addition of TiO ₂ . b) 0.5: 1

-> the absolute DHA degradation based on the DHA use concentration <= 20% (preferably <= 15%). c) 1: 1

-> the absolute DHA degradation based on the DHA usage concentration <= 40%

(preferably <= 30%, more preferably <= 20%).

> 1: 2

-> the absolute DHA degradation based on the DHA usage concentration <= 50%

(preferably <= 40%, more preferably <= 30%).

In a further embodiment of the present invention, the preparation according to the invention may contain, in addition to dihydroxyacetone, at least one further self-tanner.

Advantageous self-tanner may be used, inter alia:

HC = OHX-OH

II ² II

HC = O HC = OCH ₇ HC-O

I i

III HC-O C = O CH ₂ C = O

I

II j H ₂ CO H ₂ C-OH HC = OH ₂ C-OH

sialdehyde hydroxymethylglyoxal γ-dialdehyde erythrulose

H ₂ C-OH

HC = O 6-aldo-D-fructose ninhydrin Also to be mentioned is 5-hydroxy-1,4-naphthoquinone (juglone) which is extracted from the shells of fresh walnuts

5-hydroxy-1,4-naphthoquinone (juglone)

and 2-hydroxy-1,4-naphthoquinone (Lawson) found in henna leaves.

2-hydroxy-1,4-naphthoquinone (Lawson)

The preparations according to the invention containing dihydroxyacetone, when applied to the human skin, are prone to malodour, presumably caused by decomposition products of the dihydroxyacetone itself or by products of side reactions, which are in some cases perceived as unpleasant by the users. It has been found that these off-odors are avoided when using formaldehyde scavengers and / or flavonoids. Even with combined use with other self-tanner, as described above, the formation of off-odors can not be excluded. Therefore, the preparation according to the invention may preferably also contain formaldehyde scavengers and optionally flavonoids for improving the odor.

Preferably, the formaldehyde scavenger is selected from the group alkali metal, alkaline earth metal or ammonium bisulfite. Particularly preferred a preparation containing in combination DHA Plus, a mixture of DHA ₁ sodium bisulfite and magnesium stearate.

DHA Plus is a product blend containing sodium bisulfite, equivalent to Na ₂ S ₂ O ₅ or INCI: sodium disulfite, for the masking, elimination or neutralization of formaldehyde. The addition of sodium bisulfite in finished formulations significantly reduces or eliminates the unpleasant odor. DHA Plus is distributed by Merck, Darmstadt.

The flavonoid optionally present in the preparation according to the invention additionally acts as a stabilizer for the self-tanner or self-tanning substances and / or reduces or avoids or improves storage-dependent off-odors, which can also be caused by additives or auxiliaries.

Preferably, it is a flavonoid in which one or more phenolic hydroxy groups are blocked by etherification or esterification. For example, hydroxyethyl-substituted flavonoids, such as preferably troxerutin, troxequercetin, troxeisoquercetin or troxeluteolin, and flavonoid sulfates or flavonoid phosphates, such as preferably rutosulfates, have proven to be particularly suitable flavonoids. Particularly preferred in the context of the use according to the invention are rutin sulfate and troxerutin. Very particularly preferred is the use of troxerutin.

The preferred flavonoids have a non-positively charged Flavangrundkörper. It is believed that these flavonoids complex metal ions such as Fe ² VCu ²⁺ and thus prevent or reduce auto-oxidation processes in fragrances or compounds whose degradation leads to malodors.

Particularly preferred is a preparation containing DHA Rapid and / or sodium bisulfite. DHA Rapid is a product mixture containing dihydroxyacetone and troxerutin, Merck, Darmstadt. Corresponding premixes and preparations which contain formaldehyde scavengers and, if appropriate, flavonoids for improving the odor on the skin are described in the German patent application with the application DE 10 2007 013 368.7, the contents of which are expressly also part of the disclosure of the present application.

Furthermore, the titanium dioxides according to the invention can also be used with the following substances alone or in combination with DHA for tanning intensification:

Vegetan Premium (INCI Dihydroxyacetone / Melanin) from Soliance, - MelanoBronze (INCI: Vitex agnus castus extract (and) acetyl tyrosine (and) glycerol (and) alcohol (and) water (aqua)) Mibelle AG Biochemistry.

- Instabronze® (INCI dihydroxyacetone (DHA), N-acetyl tyrosine), Alban Müller,

Substances which promote penetration, such as e.g. Empty liposomes, propylene glycol, isohexadecane (Arlamol HD, Croda), dimethylisosorbide (Arlasolve DMI, CRODA), trimethylpentanediol / adipic acid / isononanoic acid copolymer (INCI name) or (Lexorez TC-8, Inolex).

The use of the nanoparticulate titanium dioxide according to the invention for stabilizing dihydroxyacetone or dihydroxyacetone derivatives, in particular dihydroxyacetone, is a further subject of the present invention.

Furthermore, combinations of the titanium dioxide particles according to the invention with other particulate UV filters, both as a powder and as a dispersion or paste, of the following types are also possible.

Here, both those from the group of titanium dioxides, such as coated titanium dioxide (for example Eusolex ^® T-2000, Eusolex ^® T-AQUA, Eusolex ^® T-AVO, Eusolex ^® T-OLEO), zinc oxides (eg Sachtotec® ^®), iron oxides and also Cerium oxides and / or zirconium oxides are preferred. Furthermore, combinations with pigmentary titanium dioxide or zinc oxide are also possible, the particle size of these pigments being greater than or equal to 200 nm, for example Hombitec® COS.

Furthermore, it can be preferred according to the invention if the preparations contain inorganic UV filters which are prepared by customary methods, for example in Cosmetics & Toiletries, February 1990, Vol. 105, pp. 53-64, were post-treated. Here, one or more of the following aftertreatment components may be selected: amino acids, beeswax, fatty acids, fatty acid alcohols, anionic surfactants, lecithin, phospholipids, sodium, potassium, zinc, iron or aluminum salts of fatty acids, polyethylenes, silicones, proteins (especially Collagen or elastin), alkanolamines, silica, alumina, other metal oxides, phosphates, such as sodium hexametaphosphate or glycerol.

Preferably used further particulate UV filters are:

untreated titanium dioxides such as e.g. the products Microtitanium Dioxide MT 500 B from Tayca; Titanium Dioxide P25 from Degussa,

Post-treated micronized titanium dioxides with alumina and silica. the product "Microtitanium Dioxide MT 100 SA of Tayca; or the product "Tioveil Fin" from Uniqema,

Aftertreated micronised titanium dioxides with alumina and / or aluminum stearates / laurate aftertreatment, e.g. Microtitanium Dioxide MT 100 T from Tayca, Eusolex T-2000 from Merck,

Post-treated micronized titanium dioxides with iron oxide and / or iron stearates. the product "Microtitanium Dioxide MT 100 F" from Tayca,

Aftertreated micronised titanium dioxides with silicas, alumina and silicone aftertreatment, e.g. the product "Microtitanium Dioxide MT 100 SAS", the company Tayca,

After-treated micronized titanium dioxides with Natrumhexametaphosphate, such as the product "Microtitanium Dioxide MT 150 W" Fa. Tayca. The treated micronized titanium dioxides used for combination may also be post-treated with:

Octyltrimethoxysilane; such as. the product Tego Sun T 805 from Degussa,

silica; such as. the product Parsol T-X from DSM,

Alumina and stearic acid; such as. the product UV titanium M160 from Kemira,

Aluminum and glycerin; such as. the product UV-Titan of the company Kemira,

Aluminum and silicone oils, e.g. the product UV-Titan M262 from Kemira,

Sodium hexamethaphosphate and polyvinylpyrrolidone,

Polydimethylsiloxanes, e.g. the product 70250 Cardre UF TiO2SI3 "from the company Cardre,

Polydimethylhydrogensiloxanes, e.g. Microtitanium Dioxide USP Grade Hydrophobie "from Color Techniques.

Furthermore, the combination with the following products can also be advantageous:

Untreated zinc oxides such. For example, the product Z-Cote from BASF (Sunsmart), Nanox from the company Elementis

Post-treated zinc oxides such as the following products: o "Zinc Oxide CS-5" from Toshibi (ZnO aftertreated with polymethylhydrogenosiloxanes) Nanogard Zinc Oxide FN from Nanophase Technologies o "SPD-Z1" from Shin-Etsu (ZnO aftertreated with a

Silicone-grafted acrylic polymer dispersed in cyclodimethylsiloxanes o "Escalol Z100" of the company ISP (aluminum oxide aftertreated ZnO dispersed in an ethylhexyl methoxycinnamate / PVP-hexadecenes / methicone copolymer mixture) "Fuji ZNO-SMS-10" from Fuji Pigment (ZnO aftertreated with Silica and polymethylsilsquioxane); o Untreated cerium oxide micropigment, for example with the name "Colloidal Cerium Oxide" from Rhone Poulenc o Untreated and / or post-treated iron oxides with the name Nanogar from Arnaud.

By way of example, mixtures of various metal oxides, e.g. Titanium dioxide and cerium oxide with and without Nachbenhandlung be used, such. the product Sunveil A of the company Ikeda. In addition, mixtures of alumina, silica and silicone post-treated titanium dioxide may also be used. Zinc oxide mixtures such. the product UV titanium M261 from Kemira can be used in combination with the UV protection agent according to the invention.

As a rule, these inorganic UV filters are incorporated in cosmetic preparations in an amount of from 0.1% by weight to 25% by weight, preferably 2% by weight to 10% by weight. In particular, it may be preferred if in emulsions in one phase, an inventive nanoparticulate titanium dioxide and in the other phase, a further inorganic UV filter is included.

Preferred preparations, in particular having light-protection properties, contain at least one further UV filter, in particular a dibenzoylmethane derivative. The dibenzoylmethane derivatives used in the context of the present invention are already well-known products, which are described in particular in the above-mentioned publications FR-A-2 326 405, FR-A-2 440 933 and EP-A-0 114 607. The dibenzoylmethane derivatives which can be used according to the invention can be chosen in particular from the dibenzoylmethane derivatives of the following formula:

worin R¹, R², R³ und R⁴, die identisch oder voneinander verschieden sind, Wasserstoff, eine geradkettige oder verzweigte C_1-8-Alkylgruppe oder eine geradkettige oder verzweigte C_1-8-Alkoxygruppe bedeuten. Gemäß, der vorliegenden Erfindung können selbstverständlich ein Dibenzoylmethanderivat oder mehrere Dibenzoylmethanderivate verwendet werden. Von den Dibenzoylmethanderivaten, auf die sich die vorliegende Erfindung spezieller bezieht, können insbesondere:

wherein R ¹ , R ² , R ³ and R ⁴ , which are identical or different, denote hydrogen, a straight-chain or branched C _1-8 -alkyl group or a straight-chain or branched C _1-8 -alkoxy group. According to the present invention, of course, a dibenzoylmethane derivative or a plurality of dibenzoylmethane derivatives can be used. Of the dibenzoylmethane derivatives to which the present invention more specifically relates, in particular:

2-methyldibenzoylmethane,

4-methyldibenzoylmethane,

4-isopropyldigenoylmethane,

4-tert-butyldibenzoylmethane,

2,4-dimethyldibenzoylmethane,

2,5-dimethyldibenzoylmethane,

4,4'-diisopropyldibenzoylmethane,

4,4'-methoxy-tert-butyldibenzoylmethane, 2-methyl-5-isopropyl-4'-methoxydibenzoylmethane,

2-methyl-5-tert-butyl-4'-methoxydibenzoylmethane, 2,4-dimethyl-4'-methoxydibenzoylmethane and

- 2,6-dimethyl-4-tert-butyl-4'-methoxydibenzoylmethane be mentioned, this list is not limiting.

Of the above dibenzoylmethane derivatives according to the invention, in particular the 4,4'-methoxy-t-butyldibenzoylmethane, and in particular the left under the trade name Eusolex ^® 9020 from Merck commercially 4,4'-methoxy-t-butyldibenzoylmethane, said Filter corresponds to the following structural formula:

Another preferred dibenzoylmethane derivative is 4-isopropyldibenzoylmethane. Further preferred preparations with further organic UV filters thereby contain at least one benzophenone or derivative of benzophenone, such as particularly preferably 2-hydroxy-4-methoxybenzophenone (eg

Eusolex® 4360) or 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its sodium salt (e.g., Uvinul® MS-40).

The dibenzoylmethane derivative (s) or the benzophenone derivative (s) may be present in the inventive compositions in proportions generally ranging from 0.1% to 10% by weight (by weight), and preferably in Amounts in the range of 0.3 wt .-% to 5 wt .-%, wherein these proportions are based on the total weight of the preparation.

The preparations according to the invention may of course comprise one or more additional hydrophilic or lipophilic sunscreen filters which are in the UV-A range and / or UV-B range and (/ or IR and / or VIS range (US Pat. These additional filters can be chosen in particular from cinnamic acid derivatives, salicylic acid derivatives, camphor derivatives, triazine derivatives, β, β-diphenylacrylate derivatives, p-aminobenzoic acid derivatives and polymeric filters and silicone filters described in the application WO-93/04665 Further examples of organic filters are given in the patent application EP-A 0 487 404. In the following, the named UV filters are usually named according to the INCI nomenclature.

In particular, here are:

para-aminobenzoic acid and its derivatives: PABA, ethyl PABA, ethyl dihydroxypropyl PABA, ethylhexyl dimethyl PABA, e.g. B. under the name "Escalol 507" from the company. ISP, glyceryl PABA, PEG-25 PABA ₁ z. B. under the name "Uvinul P25" from BASF.

Salicylates: Homosalates are sold under the name "Eusolex HMS" by Merck; Ethyl hexyl salicylates, e.g. B. under the name "Neo Heliopan OS" from the company. Haarmann and Reimer, Dipropylene glycol salicylate, z. B. under the name "Dipsal" from the company. Scher, TEA salicylate, z. B. under the name "Neo Heliopan TS" from the company Haarmann and Reimer. ß, ß-diphenyl acrylates Derivatives: Octocrylene, z. B. under the name "Uvinul N539" from BASF, Etocrylene, z. B. under the name "Uvinul N35" from BASF.

Benzophenone Derivatives: Benzophenone-1, e.g. B. operated under the name "Uvinul 400"; Benzophenone-2, e.g. B. operated under the name "Uvinul D50"; Benzophenone-3 or oxybenzone, e.g. B. sold under the name "Uvinul M40" Benzophenone-4, z. B. operated under the name "Uvinul MS40"; Benzophenone-9, e.g. B. under the name "Uvinul DS-49" from the company. BASF, Benzophenone-5, Benzophenone-6, z. B. under the name "Helisorb 11" from the company. Norquay, Benzophenone-8, z. B. under the name "Spectra-Sorb UV-24" from the company American Cyanamid, Benzophenone 12 n-hexyl 2- (4-diethylamino-2-hydroxybenzoyl) benzoates.

Benzylidene camphor derivatives: 3-benzylidenecamphor, e.g. B. under the name "Mexoryl SD" from the company Chimex, 4-Methylbenzylidenecamphor, z. B. under the name "Eusolex 6300" from the company Merck, Benzylidenecamphorsulfonsäure, z. B. under the name "Mexoryl SL" from the company Chimex, Camphor benzalkonium methosulfate, z. B. under the name "Mexoryl SO" from the company Chimex,

Terephthalylidenedicamphorsulfonic acid, e.g. B. sold under the name "Mexoryl SX" from the Fa Chimex, Polyacrylamidomethylbenzylidenecamphor operated under the name "Mexoryl SW" from the company Chimex.

Phenylbenzimidazole derivatives: phenylbenzimidazolesulfonic acid, e.g. B. under the name "Eusolex 232" from the company Merck, disodium phenyl dibenzimidazole tetrasulfonate, z. B. under the name "Neo Heliopan AP" from the company Haarmann and Reimer.

Phenylbenzotriazole derivatives: Drometrizole trisiloxanes, e.g. B. under the name "Silatrizole" from the Fa. Rhodia Chimie, Methylenebis (benzotriazolyl) tetramethylbutylphenol in solid form, eg. B. under the name "MIXXIM BB / 100" from the company. Fairmount Chemical, or in micronized form as an aqueous dispersion, eg. B. under the name "Tinosorb M" from the company. Ciba Specialty Chemicals. Triazines derivatives: ethylhexyltriazone, e.g. B. under the name "Uvinul T150" from the Fa. BASF, Diethylhexylbutamidotriazone, z. B. under the name "Uvasorb HEB" from the company. Sigma 3V, 2,4,6-tris (diisobutyl 4'-aminobenzalmalonate) -s-triazines.

Anthraniline derivatives: menthyl anthranilate, e.g. B. under the name "Neo Heliopan MA" from the company Haarmann and Reimer.

Imidazole derivatives: Ethylhexyldimethoxybenzylidenedioxoimidazoline propionate.

Benzalmalonate Derivatives: Polyorganosiloxanes containing functional benzalmalonate groups, e.g. Polysilicone-15, e.g. B. sold under the name "Parsol SLX" by Hoffmann LaRoche.

4,4-Diarylbutadiene derivatives: 1,1-dicarboxy (2,2'-dimethylpropyl) -4,4-diphenylbutadiene.

Benzoxazole Derivatives: 2,4-bis [5- (1-dimethylpropyl) benzoxazol-2-yl (4-phenyl) imino] -6- (2-ethylhexyl) imino-1,3,5-triazines, e.g. B. sold under the name Uvasorb K2A from the company. Sigma 3V and mixtures thereof containing.

Piperazine derivatives such as the compound

The compounds listed in the list are examples only. Of course, other UV filters can be used. In particular, organic particulate UV filters, as described, for example, in the patent application WO 99/66896, can advantageously also be combined with the particulate titanium dioxide particles according to the invention.

The organic UV-protective substances which are suitable for combination with the UV protection agent according to the invention are preferably to be selected from the following list: ethylhexyl salicylate, octocrylene, butylmethoxydibenzoylmethane, phenylbenzimidazolesulfonic acid, benzophenone-3, benzophenone-4, benzophenone-5, n-hexyl-2 (4-diethylamino-2-hydroxybenzoyl) benzoates, 4-methylbenzylidenecamphor, terephthalylidenedicamphorsulfonic acid, disodium phenyldibenzimidazoletetrasulfonates,

Methylenebis (benzotriazolyl) tetramethylbutylphenol, ethylhexyl triazone, diethylhexyl butamido triazone, drometrizole trisiloxane, polysilicone-15, 1, 1-dicarboxy (2,2'-dimethylpropyl) -4,4-diphenylbutadiene, 2,4-bis [5-1 ( dimethylpropyl) benzoxazol-2-yl (4-phenyl) imino] -6- (2-ethylhexyl) imino-1,3,5-triazines and mixtures thereof.

These organic UV filters are usually incorporated in formulations in an amount of from 0.01% to 20% by weight, preferably 1% to 10% by weight.

As a rule, organic UV filters are generally incorporated in formulations in an amount of from 0.01% by weight to 20% by weight, preferably from 0.5% by weight to 20% by weight.

Preferred formulations may also contain compounds of the formula I,

wherein R ¹ and R ^{2 are} selected from H

and OR, where OR is independently

OH straight-chain or branched C ₁ - to C ₂ o-alkoxy, straight-chain or branched C ₃ - to C ₂ o-alkenyloxy, straight-chain or branched C ₁ - to C ₂₀ -hydroxyalkoxy, wherein the hydroxy group (s) to a primary or secondary Carbon atoms of the chain may be bound and further the alkyl chain may also be interrupted by oxygen, and / or

C ₃ - to C ₁₀ -cycloalkyloxy groups and / or C ₃ - to C ₁₂ -cycloalkenyloxy groups, where the rings may each also be bridged by - (CH ₂ ) _n - groups where n = 1 to 3 and / or

Mono and / or oligoglycosyl radicals,

with the proviso that at least one of R ¹ and R ² is OR ¹¹ , and R ³ is OR ¹¹ and

R ⁴ to R ⁷ and R ^{10 may be the} same or different, and independently of one another represents

H straight or branched C ₁ - to C ₂₀ -alkyl groups, straight-chain or branched C ₃ - to C ₂ o-alkenyl groups, straight-chain or branched C ₁ - to C ₂₀ -hydroxyalkyl groups, where - the hydroxy group to a primary or secondary carbon atom of the chain may be bound and further the alkyl chain may also be interrupted by oxygen, and / or

C ₃ - to C ₁₀ -cycloalkyl groups and / or C ₃ - to C ₁₂ -cycloalkenyl groups, it also being possible for the rings to be bridged by - (CH ₂ ) _n groups where n = 1 to 3, and R ⁸ and R ^{9 may be the} same or different, and independently represent

H

OR ¹¹ straight-chain or branched C ₁ - to C ₂ o-alkyl groups, straight-chain or branched C ₃ - to C ₂ o-alkenyl groups, straight-chain or branched C ₁ - to C ₂ o-hydroxyalkyl groups, where the hydroxy group to a primary or secondary carbon atom the chain can be bound and further the alkyl chain can also be interrupted by oxygen, and / or

C ₃ - to C ₁₀ -cycloalkyl groups and / or C ₃ - to C ₁₂ -cycloalkenyl groups, it also being possible for the rings to be bridged by - (CH ₂ ) _n groups where n = 1 to 3.

Advantages of the preparations are in particular the UV light filtering effect and the good skin compatibility. In addition, the compounds of the aforementioned formula described here are colorless or only slightly colored and thus, in contrast to many known naturally occurring flavonoids, do not lead to discoloration of the preparations.

Among the flavonoids of the aforementioned formula to be used according to the invention, there are broadband UV filters, while other likewise preferred compounds of the aforementioned formula show an absorption maximum in the boundary region between the UV-B and the UV-A radiation. As UV-Al I filters, they therefore advantageously supplement the absorption spectrum of commercially available UV-B or UV-Al filters. Preferred compositions with photoprotective properties contain at least one compound of the aforementioned formula, wherein R ³ is

OH or straight-chain or branched C ₁ - to C ₂ o-alkoxy groups, preferably methoxy, ethoxy or ethylhexyloxy or

Mono- and / or Oligoglycosylreste, preferably Glucosylreste and R ¹ and / or R ² preferably represent OH or straight-chain or branched C ₁ - to C ₂₀ -alkoxy groups, preferably methoxy, ethoxy or ethylhexyloxy or

Mono- and / or Oligoglycosylreste, preferably Glucosylreste.

These preferred compounds are characterized by a particularly intense UV absorption.

In addition, such preferred compounds have advantages in the incorporation into the preparations:

Mono- and / or Oligoglycosylreste improve the water solubility of the compounds to be used according to the invention; straight-chain or branched (V to C ₂ o-alkoxy groups, in particular the long-chain alkoxy functions, such as ethylhexyloxy groups increase the oil solubility of the compounds;

i.e. By suitable selection of the substituents, the hydrophilicity or lipophilicity of the compounds can be controlled nch formula I. Preferred mono- or oligosaccharide radicals are hexosyl radicals, in particular ramnosyl radicals and glucosyl radicals. However, other hexosyl radicals, for example allosyl, altrosyl, galactosyl, gulosyl, idosyl, mannosyl and talosyl, may also be advantageous to use. It may also be advantageous to use pentosyl radicals. The glycosyl residues can be linked to the main body in α- or β-glycosidic manner. A preferred disaccharide is, for example, 6-O- (6-deoxy-α-L-mannopyranosyl) -β-D-glucopyranoside.

It has been found that the intensity of the UV absorption is high, especially when R ³ is straight-chain or branched C ₁ to C ₂ o-alkoxy groups, preferably methoxy, ethoxy or ethylhexyloxy, and R ⁸ and R ^{9 are the} same and stand for H or straight-chain or branched C ₁ - to C ₂₀ -alkoxy groups, preferably methoxy, ethoxy or ethylhexyloxy. Therefore, preparations with light protection properties comprising at least one compound of the aforementioned formula, which is characterized in that R ³ is straight-chain or branched C _r to C ₂ o-alkoxy groups, preferably methoxy, ethoxy or ethylhexyloxy, and R ⁸ and R ^{9 is the} same are and are H or straight-chain or branched C ₁ - to C ₂ o-alkoxy, preferably methoxy, ethoxy or ethylhexyloxy, particularly preferred according to the invention. In particular, it is preferred if and R ⁸ and R ⁹ stand for H.

The compounds of the aforementioned formula are typically added in amounts of from 0.01% to 20% by weight, preferably in amounts of from 0.5% to 10% by weight and most preferably in amounts of 1% by weight .-% to 8 wt .-% used. It does not cause the expert any difficulty to select the quantities depending on the intended SPF of the preparation accordingly.

By combining the titanium dioxide particles according to the invention with other UV filters, the protective action against harmful effects of the UV radiation can be optimized. For example, optimized formulations can be the combination of the organic UV filters 4 "-methoxy-6-hydroxyflavone with 1- (4-tert-butylphenyl) -3- (4-methoxyphenyl) propane-1,3-dione and 3- (4 ^'). Methylbenzylidene) -dl camphor.

All mentioned UV filters can also be used in encapsulated form. In particular, it is advantageous to use organic UV filters in encapsulated form. In detail, there are the following advantages:

- The hydrophilicity of the capsule wall can be adjusted independently of the solubility of the UV filter. For example, hydrophobic UV filters can also be incorporated into purely aqueous preparations. In addition, the often perceived as unpleasant oily impression when applying the hydrophobic UV filter containing preparation is suppressed.

Certain UV filters, in particular dibenzoylmethane derivatives, show only reduced photostability in cosmetic preparations. By encapsulating these filters or compounds that have photostability such filters, such as cinnamic acid derivatives, can increase the photostability of the entire formulation.

In the literature, the skin penetration through organic UV filters and the associated irritation potential during direct application to the human skin is discussed again and again. The encapsulation of the corresponding substances proposed here prevents this effect.

- Generally, by encapsulation of individual UV filters or other ingredients preparation problems caused by interaction of individual preparation components with each other, such as crystallization processes, precipitation and agglomeration can be avoided because the interaction is prevented.

Therefore, it may be preferred according to the invention, if one or more of the compounds of formula I or (which formula I) of the above-mentioned UV filter are present in encapsulated form. It is advantageous if the capsules are so small that they can not be observed with the naked eye. To achieve the o.g. Effects it is still necessary that the capsules are sufficiently stable and donate the encapsulated active ingredient (UV filter) not or only to a small extent to the environment.

Suitable capsules may have walls of inorganic or organic polymers. For example, US Pat. No. 6,242,099 B1 describes the preparation of suitable capsules having walls of chitin, chitin derivatives or polyhydroxylated polyamines. Capsules which are particularly preferred for use in accordance with the invention have walls which can be obtained by a sol-gel process as described in applications WO 00/09652, WO 00/72806 and WO 00/71084. Again, capsules whose walls are made up of silica gel (silica, undefined silicon oxide hydroxide) are preferred. The production of such capsules is known to the skilled worker, for example, from the cited patent applications, whose contents are expressly also part of the subject of the present application. The capsules in preparations according to the invention are preferably present in amounts which ensure that the encapsulated UV filters are present in the preparation in the amounts indicated above.

Furthermore, the preparations according to the invention may also contain dyes and colored pigments. The dyes and pigments can be selected from the corresponding positive list of the Cosmetics Regulation or EC List of cosmetic colorants. In most cases, they are identical to the food-approved dyes. Examples of advantageous color pigments are titanium dioxide, mica, iron oxides (eg Fe ₂ O ₃ , Fe ₃ O ₄ , FeO (OH)) and / or tin oxide. Advantageous dyes are, for example, carmine, Berlin blue, chrome oxide green, ultramarine blue and / or manganese violet. It is particularly advantageous to choose the dyes and / or color pigments from the following list. The Color Index Numbers (CIN) are taken from the Rowe Color Index, 3rd Edition, Society of Dyers and Colourists, Bradford, England, 1971.

It may also be favorable to choose as the dye one or more substances from the following group:

2,4-dihydroxyazobenzene, 1- (2'-chloro-4'-nitro-1'phenylazo) -2-hydroxynaphthalene, ceric red, 2- (4-sulfo-1-naphthylazo) -1-naphthol-4-sulfonic acid, Calcium salt of 2-hydroxy-1,2'-azonaphthalene-1'-sulfonic acid, calcium and barium salts of 1- (2-sulfo-4-methyl-1-phenylazo) -2-naphthylcarboxylic acid, calcium salt of 1- (2- Sulfo-1-naphthylazo) -2-hydroxynaphthalene-3-carboxylic acid, aluminum salt of 1- (4-sulfo-1-phenylazo) -2-naphthol-6-sulfonic acid, aluminum salt of 1- (4-sulfo-1-naphthylazo) -2-naphthol-3,6-disulfonic acid, 1- (4-sulfo-1-naphthylazo) -2-naphthol-6,8-disulfonic acid, aluminum salt of 4- (4-sulfo-1-phenylazo) -2- ( 4-sulfophenyl) - 5-hydroxy-pyrazolone-3-carboxylic acid, aluminum and zirconium salts of 4,5-dibromofluorescein, aluminum and zirconium salts of 2,4,5,7-tetrabromofluorescein, S ''',δ'.e'-Trachloro ^^. ΔJ-tetrabromfluorescein and its aluminum salt, aluminum salt of 2,4,5,7-tetraiodofluorescein, aluminum salt of quinophthalone-disulfonic acid, aluminum salt of indigo-disulfoic acid e, red and black iron oxide (CIN: 77 491 (red) and 77 499 (black)), iron oxide hydrate (CIN: 77492), manganese ammonium diphosphate and titanium dioxide. Also advantageous are oil-soluble natural dyes such. B. paprika extract, ß-carotene or cochineal.

Also advantageous for the purposes of the present invention are gel creams containing pearlescent pigments or interference pigments, in particular those pigments whose compatibility with dihydroxyacetone has already been established. Particularly preferred are the pearlescent pigments or interference pigments, which are based on a platelet-shaped substrate and coated with titanium dioxide and / or iron oxide (Fe ₂ O ₃ ) and optionally have a final SiO ₂ layer.

Particularly preferred pigments are, for. For example, the pigments available from Merck under the trade names Timiron®, Colorona®, Dichrona® or Sirona®.

The total amount of dyes and coloring pigments is advantageously from the range of z. B. 0.1 wt .-% to 30 wt .-%, preferably from 0.5 wt .-% to 15 wt .-%, in particular from 1, 0 wt .-% to 10 wt .-%, respectively based on the total weight of the preparations.

The protective effect against oxidative stress or against the action of radicals can be further improved if the preparations contain one or more antioxidants.

There are many known and proven substances known from the literature which can be used as antioxidants, eg amino acids (eg glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles, (eg urocaninic acid) and their derivatives, peptides such as D, L- Camosine, D-carnosine, L-carnosine and their derivatives (eg anserine), carotenoids, carotenes (eg α-carotene, β-carotene, lycopene) and their derivatives, chlorogenic acid and its derivatives, lipoic acid and derivatives thereof (eg dihydrolipoic acid), Aurothioglucose, propylthiouracil and other thiols (eg thioredoxin, glutathione, cysteine, cystine, cystamine and their glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl , γ-oleoleyl, cholesteryl and glyceryl esters) and their salts, dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and their Derivatives (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) and Sulfoximinverbindungen (eg Buthioninsulfoximine, Homocysteinsulfoximin, Buthioninsulfone, penta-, hexa-, Heptathioninsulfoximin) in very low tolerated dosages (eg pmol to mol / kg), further ( Metal) chelators, (eg α-hydroxy fatty acids, palmitic acid, phytic acid, lactoferrin), α-hydroxy acids (eg citric acid, lactic acid, malic acid), humic acid, bile acid, bile extracts, bilirubin, biliverdin, EDTA, EGTA and their derivatives, unsaturated fatty acids and their derivatives, vitamin C and derivatives (eg ascorbyl palmitate, magnesium ascorbyl phosphate, ascorbyl acetate), tocopherols and derivatives (eg vitamin E acetate), vitamin A and derivatives (eg vitamin A palmitate) and coniferyl benzoate of benzoin, rutinic acid and their derivatives, α-glycosylrutin, ferulic acid, furfurylideneglucitol, carnosine, butylhydroxytoluene, butylhydroxyanisole, nordohydroguajaretic acid, tri-hydroxybutyrophene on, quercitin, uric acid and its derivatives, mannose and its derivatives, zinc and its derivatives (eg ZnO, ZnSO ₄ ), selenium and its derivatives (eg selenium methionine), stilbenes and their derivatives (eg stilbene oxide, trans-stilbene oxide).

Suitable antioxidants are also compounds of the formulas A or B.

wherein

R ^{1 can be selected} from the group -C (O) CH ₃ , -CO ₂ R ³ , -C (O) NH ₂ and -C (O) N (R ⁴ ) ₂ ,

X is O or NH, ^'

R ^{2 is} linear or branched alkyl having 1 to 30 C atoms,

R ^{3 is} linear or branched alkyl having 1 to 20 C atoms, R ^{4 are} each independently of one another H or linear or branched alkyl having 1 to 8 C atoms,

R ^{5 is} linear or branched alkyl having 1 to 8 C atoms or linear or branched alkoxy having 1 to 8 C atoms and

R ⁶ denotes linear or branched alkyl having 1 to 8 C atoms, preferably derivatives of 2- (4-hydroxy-3,5-dimethoxybenzylidene) malonic acid and / or 2- (4-hydroxy-3,5-dimethoxybenzyl) - malonic acid, particularly preferably 2- (4-hydroxy-3,5-dimethoxybenzylidene) malonic acid-bis (2-ethylhexyl) ester (for example Oxynex ^® ST Liquid) and / or 2- (4-hydroxy-3,5-dimethoxybenzy ) malonic acid bis (2-ethylhexyl) ester (eg RonaCare ^® AP). The said compounds of formula A or B are also advantageous photostabilizers for organic UV filters, but also other photosensitive compounds, such as perfume or dyes.

Mixtures of antioxidants are also suitable for use in the cosmetic preparations according to the invention. Known and commercial mixtures mixtures are, for example comprising, as active ingredients, lecithin, L - (+) - ascorbyl palmitate and citric acid (for example (for example Oxynex ^® AP), natural tocopherols, L - (+) - ascorbyl palmitate, L- (+) - ascorbic acid and citric acid (for example Oxynex ^® K LIQUID), tocopherol extracts from natural sources, L - (+) - ascorbyl palmitate, L - (+) - ascorbic acid and citric acid (for example Oxynex ^® L LIQUID), DL-α-tocopherol, L - (+) - ascorbyl palmitate, citric acid and lecithin (eg Oxynex ^® LM) or butylhydroxytoluene (BHT), L - (+) - ascorbyl palmitate and citric acid (eg Oxynex ^® 2004).

The preparations according to the invention may contain vitamins as further ingredients. Preference is given to vitamins and vitamin derivatives selected from vitamin A, vitamin A propionate, vitamin A palmitate, vitamin A acetate, retinol, vitamin B, thiamin chloride hydrochloride (vitamin B ₁ ), riboflavin (vitamin B ₂ ), nicotinamide , Vitamin C (ascorbic acid), vitamin D, ergocalciferol (vitamin D ₂ ), vitamin E, DL-α-tocopherol, tocopherol-E-acetate, tocopherol hydrogen succinate, vitamin Ki, esculin (vitamin P active ingredient), thiamih (vitamin Bi), nicotinic acid (niacin), pyridoxine, pyridoxal, pyridoxamine, (vitamin B ₆ ), Pantothenic acid, biotin, folic acid and cobalamin (vitamin B ₁₂ ) in the cosmetic preparations according to the invention, particularly preferably vitamin A palmitate, vitamin C, DL-α-tocopherol, tocopherol-E acetate, nicotinic acid, pantothenic acid and biotin.

The preparations according to the invention may additionally contain further customary skin-sparing or skin-care active substances. In principle, these can be all active ingredients known to the person skilled in the art.

Particularly preferred active ingredients are pyrimidinecarboxylic acids and / or aryloximes.

In this case, a pyrimidinecarboxylic acid according to formula II below is preferably used,

wherein R ^{1 is} a radical H or CI-8-alkyl, R ^{2 is} a radical H or C 1-4 -alkyl and R ³ , R ⁴ , R ⁵ and R ^{6 are} each independently a radical from the group H, OH, NH ₂ and C1-4 alkyl. Preference is given to using pyrimidinecarboxylic acids in which R ^{2 is} a methyl or an ethyl group and R ¹ or R ⁵ and R ^{6 are} H. Particularly preferred are the pyrimidinecarboxylic acids ectoine ((S) -1, 4,5,6-tetrahydro-2-methyl-4-pyrimidine-carboxylic acid) and hydroxyectoine ((S, S) -1, 4,5,6-tetrahydro-) 5-hydroxy-2-methyl-4-pyrimidine-carboxylic acid). The preparations according to the invention contain such

Pyrimidincarbonsäuren preferably in amounts up to 15 wt .-%.

Among the aryl oximes, 2-hydroxy-5-methyllaurophenone oxime, which is also referred to as HMLO, LPO or F5, is preferably used. Its suitability for use in cosmetic products is known for example from the German patent application DE-A-41 16 123. Preparations containing 2- Accordingly, hydroxy-5-methyllaurophenonoxime, are suitable for the treatment of skin diseases that accompany inflammation. It is known that such preparations can be used, for example, for the therapy of psoriasis, different forms of eczema, irritative and toxic dermatitis, UV dermatitis and other allergic and / or inflammatory diseases of the skin and the skin appendages. Preparations according to the invention which contain aryloximes, preferably 2-hydroxy-5-methyllaurophenone oxime, show surprising antiinflammatory suitability. The preparations preferably contain 0.01% by weight to 10% by weight of the aryloxime, and it is particularly preferred if the preparation contains from 0.05% by weight to 5% by weight of aryloxime.

All of the compounds or components described herein which may be used in the compositions are either known and commercially available or may be synthesized by known methods.

The preparations according to the invention can be prepared by processes which are well known to the person skilled in the art, in particular by the processes which are used for the preparation of oil-in-water emulsions or water-in-oil emulsions.

Another object of the present invention is a process for the preparation of a preparation, which is characterized in that titanium dioxide particles, as described above, with a cosmetically or dermatologically suitable carrier and optionally weiteen ingredients, as described above, is mixed.

These preparations may be present in particular in the form of simple or complicated emulsions (O / W, W / O, O / W / O or W / O / W), such as creams, milks, gels or gel creams, powders and solid sticks and optionally, they may be formulated as aerosols and in the form of foams or sprays. Preferably, these preparations are in the form of an O / W emulsion.

The cosmetic preparations according to the invention can be used as a preparation for protecting the human epidermis or the hair against UV radiation, used for skin care, as sunscreen, self-tanning or make-up products.

It should be noted that in the sunscreen formulations according to the invention which comprise a carrier of the oil-in-water type, the aqueous phase (which in particular contains the hydrophilic filters) is generally from 50% by weight to 95% by weight % and preferably 70% to 90% by weight, based on the total formulation, of the oil phase (containing in particular the lipophilic filters) 5% by weight to 50% by weight and preferably 10% by weight. % to 30 wt .-%, based on the total formulation and the (co) emulsifier or the (co) emulsifiers 0.5 wt .-% to 20 wt .-% and preferably 2 wt .-% to 10 wt. %, based on the total formulation.

Suitable preparations for external use, for example as a cream, lotion, gel, or as a solution that can be sprayed on the skin. For internal use, administration formulas such as capsules, dragees, powders, tablet solutions or solutions are suitable.

As an application form of the preparations according to the invention, e.g. called: solutions, suspensions, emulsions, PIT emulsions, pastes, ointments, gels, creams, lotions, powders, soaps, surfactant-containing cleaning preparations, oils, aerosols and sprays. Other applications are e.g. Sticks, shampoos and shower baths. Any customary carrier substances, adjuvants and optionally further active ingredients can be added to the preparation.

Preferable excipients come from the group of preservatives, antioxidants, stabilizers, solubilizers, vitamins, colorants, odor improvers.

Ointments, pastes, creams and gels may contain the usual excipients, for example animal and vegetable fats, waxes, paraffins, starch, tragacanth, cellulose derivatives, polyethylene glycols, silicones, bentonites, silicic acid, talc and zinc oxide or mixtures of these substances. Powders and sprays may contain the usual excipients, for example lactose, talc, silicic acid, aluminum hydroxide, calcium silicate and polyamide powder or mixtures of these substances. Sprays may additionally contain the customary propellants, for example chlorofluorohydrocarbons, propane / butane or dimethyl ether.

Solutions and emulsions may contain the usual excipients such as solvents, solubilizers and emulsifiers, e.g. Water, ethanol, isopropanol, ethyl carbonate, ethyl acetate, benzyl alcohol, benzyl benzoate, propylene glycol, 1, 3-butylglycol, oils, in particular cottonseed oil, peanut oil, corn oil, olive oil, castor oil and sesame oil, glycerin fatty acid esters, polyethylene glycols and fatty acid esters of sorbitan or mixtures of these substances contain.

Suspensions may include the usual carriers such as liquid diluents, e.g. Water, ethanol or propylene glycol, suspending agents, e.g. ethoxylated isostearyl alcohols, polyoxyethylene sorbitol esters and polyoxyethylene sorbitan esters, microcrystalline cellulose, aluminum metahydroxide, bentonite, agar-agar and tragacanth or mixtures of these substances.

Soaps may contain the usual excipients such as alkali metal salts of fatty acids, salts of fatty acid monoesters, fatty acid protein hydrolysates, isothionates, lanolin, fatty alcohol, vegetable oils, plant extracts, glycerol, sugars or mixtures of these substances.

Surfactant-containing cleaning products may contain the usual excipients such as salts of fatty alcohol sulfates, fatty alcohol ether sulfates, sulfosuccinic monoesters, fatty acid protein hydrolysates, isothionates, imidazolinium derivatives, methyl taurates, sarcosinates, fatty acid amide ether sulfates, alkylamidobetaines, fatty alcohols, fatty acid glycerides, fatty acid diethanolamides, vegetable and synthetic oils, lanolin derivatives, ethoxylated glycerol fatty acid esters or mixtures of these substances.

Facial and body oils may contain the usual excipients such as synthetic oils such as fatty acid esters, fatty alcohols, silicone oils, natural oils such as vegetable oils and oily vegetable extracts, paraffin oils, lanolin oils or mixtures of these substances. Other typical cosmetic application forms are also lipsticks, lip balms, mascara, eyeliner, eye shadow, rouge, powder, emulsion and wax make-up and sunscreen, pre-sun and after-sun preparations.

The preferred preparation forms according to the invention include in particular emulsions.

Emulsions of the invention are advantageous and contain z. As mentioned fats, oils, waxes and other fatty substances, and water and an emulsifier, as it is commonly used for such a type of preparation.

The lipid phase can advantageously be selected from the following substance group:

- mineral oils, mineral waxes

- Oils such as triglycerides of capric or caprylic, further natural oils such. Castor oil;

Fats, waxes and other natural and synthetic fats, preferably esters of fatty acids with lower C-number alcohols, e.g. with isopropanol, propylene glycol or glycerol, or esters of fatty alcohols with low C-alkanoic acids or with fatty acids;

- Silicone oils such as dimethylpolysiloxanes, diethylpolysiloxanes, diphenylpolysiloxanes and mixed forms thereof.

The oil phase of the emulsions, oleogels or hydrodispersions or lipodispersions in the context of the present invention is advantageously selected from the group of esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids having a chain length of 3 to 30 carbon atoms and saturated and / or or unsaturated, branched and / or unbranched alcohols having a chain length of 3 to 30 carbon atoms, from the group of esters of aromatic carboxylic acid and saturated and / or unsaturated, branched and / or unbranched alcohols having a chain length of 3 to 30 carbon atoms. Such ester oils can then advantageously be selected from the group isopropyl myristate, isopropyl palmitate, isopropyl stearate, isopropyl oleate, n-butyl stearate, n-hexyl laurate, n-decyl oleate, isooctyl stearate, isononyl stearate, isononyl isononanoate, 2-ethylhexyl palmitate, 2-ethylhexyl laurate, 2-hexadecyl stearate, 2 Octyl dodecyl palmitate, oleyl oleate, oleyl erucate, erucyl oleate, Erucylerucat and synthetic, semi-synthetic and natural mixtures of such esters, eg. B. jojoba oil.

Furthermore, the oil phase can advantageously be selected from the group of branched and unbranched hydrocarbons and waxes, silicone oils, dialkyl ethers, the group of saturated or unsaturated, branched or unbranched alcohols, and fatty acid triglycerides, in particular the triglycerol esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids of a chain length of 8 to 24, in particular 12-18 C-atoms. The fatty acid triglycerides can be selected, for example, advantageously from the group of synthetic, semi-synthetic and natural oils, for. For example, olive oil, sunflower oil, soybean oil, peanut oil, rapeseed oil, almond oil, palm oil, coconut oil, palm kernel oil and the like.

Any mixtures of such oil and wax components are also advantageous to use in the context of the present invention. It may also be advantageous, if appropriate, to use waxes, for example cetyl palmitate, as the sole lipid component of the oil phase.

The oil phase is advantageously selected from the group 2-ethylhexyl isostearate, octyldodecanol, isotridecyl isononanoate, isoeicosane, 2-ethylhexyl cocoate, C _12-15 - alkyl benzoate, caprylic capric triglyceride, dicapryl ether.

Particularly advantageous are mixtures of C ₂ -i ₅ alkyl benzoate and 2-ethylhexyl isostearate, mixtures of C ₁₂ -i ₅ alkyl benzoate and isotridecyl isononanoate and mixtures of C- | ₂ -i ₅ -alkyl benzoate, 2-ethylhexyl isostearate and isotridecyl isononanoate.

Of the hydrocarbons, paraffin oil, squalane and squalene are to be used advantageously in the context of the present invention.

Advantageously, the oil phase can also have a content of cyclic or linear silicone oils or consist entirely of such oils, although it is preferred to use an additional content of other oil phase components in addition to the silicone oil or silicone oils. Advantageously, cyclomethicone (octamethylcyclotetrasiloxane) is used as the silicone oil to be used according to the invention. However, other silicone oils are also advantageous for the purposes of the present invention, for example hexamethylcyclotrisiloxane, polydimethylsiloxane,

Poly (methylphenylsiloxane).

Also particularly advantageous are mixtures of cyclomethicone and Iso tridecylisononanoat, from cyclomethicone and 2-Ethylhexylisostearat.

If appropriate, the aqueous phase of the preparations according to the invention advantageously contains alcohols, diols or polyols of low C number, and their ethers, preferably ethanol, isopropanol, propylene glycol, glycerol, ethylene glycol, ethylene glycol monoethyl or monobutyl ether, propylene glycol monomethyl, monoethyl or monobutyl ether , Diethylene glycol monomethyl or monoethyl ether and analogous products, furthermore lower C number alcohols, e.g. As ethanol, isopropanol, 1, 2-propanediol, glycerol and in particular one or more thickening agents, which or which can be advantageously selected from the group of silica, aluminum silicates, polysaccharides or their derivatives, e.g. Hyaluronic acid, xanthan gum,

Hydroxypropylmethylcellulose, particularly advantageous from the group of polyacrylates, preferably a polyacrylate from the group of so-called Carbopole, for example, Carbopols types 980, 981, 1382, 2984, 5984, each individually or in combination.

In particular, mixtures of the abovementioned solvents are used. For alcoholic solvents, water can be another ingredient.

Emulsions of the invention are advantageous and contain z. As mentioned fats, oils, waxes and other fatty substances, and water and an emulsifier, as it is commonly used for such a type of formulation.

In a preferred embodiment, the preparations according to the invention contain hydrophilic surfactants.

The hydrophilic surfactants are preferably selected from the group of alkylglucosides, acyl lactylates, betaines and cocoamphoacetates. Alkylglylcosides used particularly advantageously according to the invention are chosen from the group octylglucopyranoside, nonylglucopyranoside, decylglucopyranoside, undecylglucopyranoside, dodecylglucopyranoside, tetradecylglucopyranoside and hexadecylglucopyranoside.

It is likewise advantageous to employ natural or synthetic raw materials and assistants or mixtures which are distinguished by an effective content of the active ingredients used according to the invention, for example Plantaren ^® 1200 (Henkel KGaA), Oramix NS ^® 10 (Seppic).

In turn, the acyl lactylates are advantageously selected from the group of substances which are defined by the structural formula

O O

IVP

in which R ^{1 is} a branched or unbranched alkyl radical having 1 to 30 carbon atoms and M ^{+ is selected} from the group of the alkali metal ions and the group of ammonium ions substituted by one or more alkyl and / or by one or more hydroxyalkyl radicals or half Equivalent to an alkaline earth metal equivalent.

For example, sodium is advantageous, for example the product Pathionic ^® ISL from the American Ingredients Company.

For the group of betaine, for example capramidopropylbetaine advantageous for example the product Tego ^® betaine 810 from Th. Goldschmidt AG. AIs invention advantageous cocoamphoacetate, sodium is selected, for example, as under the name Miranol ^® Ultra C32 from Miranol Chemical Corp. is available.

The preparations according to the invention are advantageously characterized in that the hydrophilic surfactant or surfactants in concentrations of 0.01-20 wt .-%, preferably 0.05-10 wt .-%, particularly preferably 0.1-5 wt .-%, respectively based on the total weight of the preparation, is present or present.

For use, the cosmetic and dermatological preparations according to the invention are applied to the skin and / or the hair in a sufficient amount in the manner customary for cosmetics.

Cosmetic and dermatological preparations according to the invention can be present in various forms. So they can z. For example, a solution, an anhydrous preparation, an emulsion or microemulsion of the water-in-oil (W / O) type or of the oil-in-water (O / W) type, a multiple emulsion, for example of the Waser-in type. Oil-in-water (W / O / W), a gel, a solid stick, an ointment or even an aerosol. It is also advantageous to present Ectoine in encapsulated form, e.g. In collagen matrices and other common encapsulating materials, e.g. As encapsulated cellulose, in gelatin, wax matrices or liposomally encapsulated. In particular wax matrices as described in DE-OS 43 08 282, have been found to be favorable. Preference is given to emulsions. O / W emulsins are especially preferred. Emulsions, W / O emulsions and O / W emulsions are available in the usual way.

As emulsifiers, for example, the known W / O and O / W emulsifiers can be used. It is advantageous to use further customary co-emulsifiers in the preferred O / W emulsions according to the invention.

The particularly preferred emulsifier for O / W emulsions according to the invention is the commercial product Ceralution C from Sasol. Advantageously used according to the invention as co-emulsifiers are, for example, O / W emulsifiers, primarily from the group of substances having HLB values of 11-16, very particularly advantageously having HLB values of 14.5-15.5, provided that the O / W emulsifiers have W emulsifiers have saturated radicals R and R ¹ . If the O / W emulsifiers have unsaturated radicals R and / or R ', or if isoalkyl derivatives are present, the preferred HLB value of such emulsifiers may also be lower or higher.

It is advantageous to choose the fatty alcohol ethoxylates from the group of ethoxylated stearyl alcohols, cetyl alcohols, cetylstearyl alcohols (cetearyl alcohols). Particularly preferred are: polyethylene glycol (13) stearyl ether (steareth-13), polyethylene glycol (14) stearyl ether (steareth-14), polyethylene glycol (15) stearyl ether (steareth-15), polyethylene glycol (16) stearyl ether (steareth-16), polyethylene. glycol (17) stearyl ether (steareth-17), polyethylene glycol (18) stearyl ether (steareth-18), polyethylene glycol (19) stearyl ether (steareth-19), polyethylene glycol (20) stearyl ether (steareth-20), polyethylene glycol (12) isostearyl ether (isosteareth-12), polyethylene glycol (13) isostearyl ether (isosteareth-13), polyethylene glycol (14) - isostearyl ether (isosteareth-14), polyethylene glycol (15) isostearyl ether

(isosteareth-15), polyethylene glycol (16) isostearyl ether (isosteareth-16),

Polyethylene glycol (17) isostearyl ether (isosteareth-17),

Polyethylene glycol (18) isostearyl ether (isosteareth-18), polyethylene glycol (19) isostearyl ether (isosteareth-19), polyethylene glycol (20) isostearyl ether (isosteareth-20), polyethylene glycol (13) cetyl ether (ceteth-13), polyethylene glycol ( 14) cetyl ether (ceteth-14), polyethylene glycol (15) cetyl ether (ceteth-15), polyethylene glycol (16) cetyl ether (ceteth-16), polyethylene glycol (17) cetyl ether (ceteth-17), polyethylene glycol (18) cetyl ether (ceteth- 18), polyethylene glycol (19) cetyl ether (ceteth-19), polyethylene glycol (20) cetyl ether (ceteth-20), polyethylene glycol (13) isocetyl ether (isoceteth-13),

Polyethylene glycol (14) isocetyl ether (isoceteth-14), polyethylene glycol (15) isocetyl ether (isoceteth-15), polyethylene glycol (16) isocetyl ether (isoceteth-16), polyethylene glycol (17) isocetyl ether (isoceteth-17), polyethylene glycol ( 18) isocetyl ether (isoceteth-18), polyethylene glycol (19) isocetyl ether (isoceteth-19), polyethylene glycol (20) isocetyl ether (isoceteth-20), polyethylene glycol (12) oleyl ether (oleth-12), polyethylene glycol (13) oleyl ether ( Oleth-13), polyethylene glycol (14) oleyl ether (Oleth-14), polyethylene glycol (15) oleyl ether (Oleth-15), polyethylene glycol (12) lauryl ether (Laureth-12), polyethylene glycol (12). isolethyl ether (isoleaureth-12), polyethylene glycol (13) cetyl stearyl ether (ceteareth-13), polyethylene glycol (14) cetyl stearyl ether (ceteareth-14), polyethylene glycol (15) cetyl stearyl ether (ceteareth-15), polyethylene glycol (16) cetyl stearyl ether (ceteareth- 16), polyethylene glycol (17) cetyl stearyl ether (ceteareth-17),

Polyethylene glycol Ki δ cetyl stearyl ether (ceteareth-18), polyethylene glycol (19) cetyl stearyl ether (ceteareth-19), polyethylene glycol (20) cetyl stearyl ether (ceteareth-20).

It is also advantageous to choose the fatty acid ethoxylates of the following group:

Polyethylene glycol (20) stearate, polyethylene glycol (21) stearate, polyethylene glycol (22) stearate, polyethylene glycol (23) stearate, polyethylene glycol (24) stearate, polyethylene glycol (25) stearate, polyethylene glycol (12) isostearate, polyethylene glycol (13) isostearate, polyethylene glycol ( 14) isostearate, polyethylene glycol (15) isostearate, polyethylene glycol (16) isostearate, polyethylene glycol (17) isostearate, polyethylene glycol (18) isostearate, polyethylene glycol (19) isostearate, polyethylene glycol (20) isostearate, polyethylene glycol (21) isostearate, polyethylene glycol (22) isostearate, polyethylene glycol (23) isostearate, polyethylene glycol (24) isostearate, polyethylene glycol (25) isostearate, polyethylene glycol (12) oleate, polyethylene glycol (13) oleate, polyethylene glycol (14) oleate, polyethylene glycol (15) oleate, polyethylene glycol (16) oleate, Polyethylene glycol (17) oleate, polyethylene glycol (18) oleate, polyethylene glycol (19) oleate, polyethylene glycol (20) oleate,

As the ethoxylated alkyl ether carboxylic acid or its salt, the sodium laureth-11-carboxylate can be advantageously used. As the alkyl ether sulfate, sodium laureth-4 sulfate can be advantageously used. As the ethoxylated cholesterol derivative, polyethylene glycol (30) cholesteryl ether can be advantageously used. Also polyethylene glycol (25) soybean oil has been proven. As ethoxylated triglycerides, the polyethylene glycol (βO) Evening Primrose Glycerides can advantageously be used (Evening Primrose = evening primrose).

It is furthermore advantageous to use the polyethylene glycol glycerol fatty acid esters from the group consisting of polyethylene glycol (20) glyceryl laurate, polyethylene glycol (21) glyceryl laurate, Polyethylene glycol (22) glyceryl laurate, polyethylglycol (23) glyceryl laurate,

Polyethylene glycol (6) glyceryl caprate / cprinate, polyethylene glycol (20) glyceryl oleate, polyethylene glycol (20) glyceryl isostearate, polyethylene glycol (18) glyceryl oleate (cocoate).

It is also favorable to use the sorbitan esters from the group consisting of polyethylene glycol (20) sorbitan monolaurate, polyethylene glycol (20) sorbitan monostearate,

Polyethylene glycol (20) sorbitan monoisostearate, polyethylene glycol (20) sorbitan monopalmitate, polyethylene glycol (20) sorbitan monooleate.

As optional, but according to the invention optionally advantageous W / O emulsifiers can be used:

Fatty alcohols having 8 to 30 carbon atoms, monoglycerol esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids of a chain length of 8 to 24, in particular 12-18 C atoms, diglycerol esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids of one chain length from 8 to 24, in particular 12-18 C-, monoglycerol ethers of saturated and / or unsaturated, branched and / or unbranched alcohols of a chain length of 8 to 24, in particular 12-18 C-atoms, diglycerol ether saturated and / or unsaturated, branched and / or unbranched alcohols of a chain length of 8 to 24, in particular 12- 18 C-atoms, propylene glycol esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids of a chain length of 8 to 24, in particular 12-18 C-atoms and sorbitan esters saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids of a Chain length of 8 to 24, in particular 12-18 C atoms.

Particularly advantageous W / O emulsifiers are glyceryl monostearate, glyceryl monoisostearate, glyceryl monomyristate, glyceryl monooleate,

Diglyceryl monostearate, diglyceryl monoisostearate, propylene glycol monostearate, propylene glycol monoisostearate, propylene glycol monocaprylate,

Propylene glycol monolaurate, sorbitan monoisostearate, sorbitan monolaurate, sorbitan monocaprylate, sorbitan monoisooleate, sucrose distearate, cetyl alcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol, isobehenyl alcohol, Selachyl alcohol, chimyl alcohol, polyethylene glycol (2) stearyl ether (steareth-2), glyceryl monolaurate, glyceryl monocaprinate, glyceryl monocaprylate.

Preparations preferred according to the invention are particularly suitable for protecting human skin against UV-induced aging processes as well as against oxidative stress, i. against damage by radicals, as e.g. be generated by sunlight, heat or other influences. It is present in various dosage forms commonly used for this application. Thus, it can be used in particular as a lotion or emulsion, such as cream or milk (O / W, W / O, O / W / O, W / O / W), in the form of oily-alcoholic, oily-aqueous or aqueous-alcoholic gels or solutions, be present as solid pins or formulated as an aerosol.

The preparation may contain cosmetic adjuvants which are commonly used in this type of preparation, e.g. Thickening agents, emollients, humectants, surfactants, emulsifiers, preservatives, antifoaming agents, perfumes, waxes, lanolin, propellants, dyes and / or pigments which color the agent itself or the skin, and other ingredients commonly used in cosmetics.

It is possible to use as dispersion or solubilizing agent an oil, wax or other fatty substance, a low monoalcohol or a low polyol or mixtures thereof. Particularly preferred monoalcohols or polyols include ethanol, i-propanol, propylene glycol, glycerine and sorbitol.

A preferred embodiment of the invention is an emulsion which is present as a protective cream or milk and in addition to the compound or compounds of formula I, for example fatty alcohols, fatty acids, fatty acid esters, especially triglycerides of fatty acids, lanolin, natural and synthetic oils or waxes and emulsifiers in the presence of Contains water.

Further preferred embodiments are oily lotions based on natural or synthetic oils and waxes, lanolin, fatty acid esters, in particular triglycerides of fatty acids, or oily-alcoholic lotions based on a lower alcohol, such as ethanol, or a glycerol, such as Propylene glycol, and / or a polyol such as glycerol, and oils, waxes and fatty acid esters, such as triglycerides of fatty acids.

The preparation according to the invention may also be in the form of an alcoholic gel which comprises one or more lower alcohols or polyols, such as ethanol, propylene glycol or glycerol, and a thickening agent, such as silica. The oily-alcoholic gels also contain natural or synthetic oil or wax.

The solid sticks consist of natural or synthetic waxes and oils, fatty alcohols, fatty acids, fatty acid esters, lanolin and other fatty substances.

If a preparation is formulated as an aerosol, the customary propellants, such as alkanes, fluoroalkanes and chlorofluoroalkanes, are generally used.

The cosmetic preparation may also be used to protect the hair against photochemical damage to prevent changes in hues, discoloration or damage of a mechanical nature. In this case, it is suitably carried out as a shampoo, lotion, gel or emulsion for rinsing, wherein the respective preparation before or after shampooing, before or after dyeing or decolorization or before or after the perm is applied. It is also possible to choose a preparation as a lotion or gel for hairdressing and treatment, as a lotion or gel for brushing or laying a wave of water, as hair lacquer, perming agent, dyeing or decolorizing the hair. The photoprotective composition may contain various adjuvants used in this type of mediator, such as surfactants, thickeners, polymers, emollients, preservatives, foam stabilizers, electrolytes, organic solvents, silicone derivatives, oils, waxes, anti-grease agents, dyes and / or pigments the agent itself or the hair dye or other commonly used for hair care ingredients.

The preparations as described above may contain, comprise, consist essentially of or consist of the necessary or optional ingredients mentioned. In the following the invention will be explained in more detail by means of examples.

Examples

Example of SiO ₂ determination or determination of the after-treatment substance containing Si.

0.1 g to 0.5 g of the sample (weighed accurately to 0.0001), depending on the expected content of Si, are mixed in a small platinum crucible with 5 g of soda / borax mixture 7 + 1 and digested for about 30 minutes. After cooling, leached out to the melt in 50 ml of dilute hydrochloric acid cold, transferred the approach in a 250 ml volumetric flask, filled up with double-distilled water to the brand and gently shakes (CO ₂ ) by. Depending on the content, the determination of the silica is carried out either directly or after appropriate dilution (the maximum digesting agent concentration for the measurement on the ICP-OES is 2%). A chemical blanket is mandatory.

Calibration is performed using standard solutions whose matrix corresponds to the sample matrix.

The device (ICP-OES) from Perkin Elmer, Optima 3300DV, is measured using the operating instructions of the device. The SiO 2 content is determined here on the total particles, ie the values are below the specified values for the SiO ₂ content based on the TiO ₂ content of the particles to be coated.

For the calculation Si - »SiO2 2.119

SiO 2 * 1, 220 = simethicone

Reagents and solutions used:

Soda, anhydrous, p.a.

Borax, sodium tetraborate, p.a.

Hydrochloric acid, diluted 1 + 1 with double-distilled water Example 1 Preparation of nano-TiO ₂ without hydrothermal treatment as comparison:

Example 1a: Preparation of a Titanium Dioxide with Iron Doping and 35%

SiO ₂ post-treatment x I of an aqueous suspension of metatitanic acid with a content of approximately

370 g of TiO ₂ / l are mixed with 0.9 g / l of water and 50 l of sodium hydroxide solution, heated to boiling temperature with stirring and kept at the temperature for 2 h.

The resulting sodium titanate is washed and washed with water to a

Content of about 100 - 110 g TiO ₂ / l set.

The titanate is heated to 60 ⁰ C. It is then acidified with 30% HCl to pH 2, then stirred for 45 min at the temperature and the pH.

An amount of a known FeCl ₃ solution is added such that the

Content of Fe is 0.09% based on TiO ₂ .

Washed with water and 30% hydrochloric acid are then adjusted levels of 45 g / l of HCl and 90 g TiO ₂ / l, and the suspension kept under stirring for 6 h at 85 ⁰ C ( "peptization").

The peptized suspension is slowly neutralized to pH 5.5 with 50% NaOH and diluted to 50 g / L.

Subsequently, the suspension at 80 ^° C with sodium silicate solution

(Concentration: about 270 g of SiO ₂ / l) and the resulting increasing pH value with dilute sulfuric acid kept constant at pH 9.0.

After addition of the entire waterglass solution with H ₂ SO _4, a pH of

6.5 and the suspension ripened for 2 h at the temperature and the pH with stirring. The suspension obtained contains about 6.7%

Product.

Example 1b:

The test product obtained from Example 1a is filtered off and washed with water to a conductivity <100 μS / cm. The resulting filter cake contains about 18% product.

Example 1c:

The test product obtained from Example 1 b is dried. It is a hydrophilic TiO ₂ with 35% silica. Example 2: Preparation of nano-TiO ₂ with hydrothermal treatment

Preparation of a hydrothermally treated titanium dioxide with iron doping and 35% SiO ₂ post-treatment: x I of an aqueous suspension of metatitanic acid containing about 370 g TϊCyi be mixed with 0.9 x I water and x I 50% sodium hydroxide solution Stirring heated to boiling temperature and kept at the temperature for 2 h. The resulting sodium titanate is washed and treated with water to a content of about 100 - 110 g TiO ₂ /! set.

The titanate is heated to 60 ⁰ C. It is then acidified with 30% HCl to pH 2, then stirred for 45 min at the temperature and the pH. With water and 30% hydrochloric acid, contents of 45 g HCl / l and 90 g TiO ₂ /! adjusted and kept the suspension with stirring for 6 h at 85 ⁰ C ("peptization").

The peptized suspension is slowly neutralized with 50% NaOH to pH 5.5 and diluted to 50 g / l and subjected to a hydrothermal treatment in the pressure vessel at 180 ⁰ C for a period of 2 h. Subsequently, the suspension is mixed at 80 ^° C. with sodium water-glass solution (concentration: about 270 g of SiO ₂ / l) and the resulting increasing pH is kept constant at pH 9.0 with dilute sulfuric acid. After addition of the entire waterglass solution, a pH of 6.5 is set with H ₂ SO ₄ and the suspension is allowed to mature for 2 hours at the temperature and the pH with stirring. The product is filtered off and washed with water to a conductivity <100 μS / cm. The resulting filter cake is slurried with water and contains about 10.5% product.

Example 2a:

3.8 kg of the washed suspension from Example 2 are dried and ground. The product is a hydrophilic TiO ₂ (hydrothermally treated) with 35% silica.

Example 2b: Post-treatment with simethicone

To 3.8 kg of the washed suspension from example 2a (corresponding to 402 g of starting product), 134 g of Silsoft Simethicone Emulsion, Fa. Momentive (30% simethicone) (corresponding to 10% of active substance, based on starting material) are slowly added with stirring and for 30 Stirred for another minute. The Suspension is dried and ground. The product is a hydrophobic TiO ₂ with 35% silica and 10% simethicone.

Example 3:

Example 3a: Compatibility with DHA in cosmetic formulation - discoloration after storage for 3 months at room temperature in the dark:

O / W test formulation used:

Trade name INCI

%%

A

inventive

5.00 1.00 TiO ₂

GLYCERYL STEARATE, STEARETH-25,

Tego Care 150 8,00 8,00 CETETH-20; STEARYL ALCOHOL

Lanette O CETEARYL ALCOHOL 1,50 1,50

CETEARYL

Tegosoft liquid 5,00 5,00 ETHYLHEXANOATE CAPRYC / CAPRYLIC Miglyol 812N 5,00 5,00 TRIGLYVCERIDE STEAROXY Abil-Wax 2434 1,00 1,00 DIMETHICONE

DC 200 (100cs) DIMETHICONE 0,50 0,50

Propylparaben PROPYLPARABEN 0,05 0,05

B

1, 2-Propanediol PROPYLENE GLYCOL 3.00 3.00

Methylparaben METHYL PARABEN 0, 15 0, 15

Water AQUA 55.80 62.80

C

DHA DIHYDROXYACETONE 5,00 2,00

Water AQUA 10.00 10.00

100.00 100.00 For the storage test, the above-mentioned test formulation with 5% by weight of DHA together with different titanium dioxide qualities is investigated:

1.5% by weight of pure DHA without TiO ₂

2. 5 wt .-% DHA with 5 wt .-% TiO ₂ according to Example 2a

3. 5% by weight of DHA with 5% by weight of TiO ₂ Example 3a

4. 5% by weight of DHA with 5% by weight of Parsol T-X

5. 5% by weight of DHA with 5% by weight of UV titanium M 263

The formulations are examined in the Minolta Chromameter CR-400 (illuminant C, observer 2 °) and show the following values:

The market products used (test formulations 4 and 5) show a strong discoloration after storage for 3 months at 40 ^° C. The particulate titanium dioxides according to the invention are visually unchanged with slight deviations from test formulation 1.

Example 3b: DHA degradation in test formulations

Glycerol Dehydrogenase

DHA is analyzed by an enzymatic determination method and is based on the following reaction:

Glycerol dehydrogenase

Dihydroxyacetone + NADH NAD ⁺ + glycerol

X _n - ,,, = 365nm λ _ma = 260 nm NADH = reduced nicotinamide adenine dinucleotide.

reagents:

Dihydroxyacetone (Merck), glycylglycine (Merck), (NH ₄ ) ₂ SO ₄ (Merck), sucrose (Merck), NADH-Na ₂ (Merck), di-sodium hydrogen phosphate dihydrate (Merck), sodium dihydrogen phosphate dihydrate (Merck), zinc chloride (Merck), glycerol dehydrogenase (Unitika Enzyms LTD).

DHA assay:

Determination of DHA concentration in a formulation based on the enzymatic DHA assay described below is based on the following reaction of dihydroxyacetone:

DHA + NADH + H + - »NAD + + glycerol

NADH shows an absorption coefficient of 365 nm. The enzyme glycerol dehydrogenase catalyses the above-mentioned reaction of dihydroxyacetone with NADH. The more DHA present, the more NADH is reacted in the reaction, and the NADH absorption at 365 nm decreases.

A. Sample Buffer Solution: Dissolve 1, 06g glycylglycine, 0.42g (NH ₄ ) ₂ SO _4, and 10.0g sucrose in demineralised water and adjust the pH to 9.0 with NaOH solution (10%) and dilute the pH Sample filled to a volume of 100ml.

B. NADH - Na ₂ solution: 0.060 g of NADH-Na ₂ is dissolved in 10.0 ml of demineralized water.

C. Buffer for the glycerol dehydrogenase solution: a. 4.43 g of di-sodium hydrogen phosphate, b. 3.90 g sodium dihydrogen phosphate dihydrate, c. 100.0 g sucrose d. 0.003 g of zinc chloride.

All the substances mentioned are dissolved in 800 ml of demineralized water and the solution is adjusted to a pH of 7.0 with 1 N hydrochloric acid or sodium hydroxide solution. Thereafter, the volume of the sample is made up to 1000 ml with demineralized water.

D. Glycerol dehydrogenase solution: 10 mg glycerol dehydrogenase in 1 ml glycerol dehydrogenase buffer (solution C).

E. DHA Standards: 0.200 g DHA (Art. No. 1.10150 Merck) is dissolved in 100 ml demineralized water. This solution is diluted 1:10. The standard is produced twice, independently of each other. The deviation of both standards from the therotic DHA content must be 100% +/- 5%.

Sample preparation:

0.5 g - 1.0 g of the test emulsion is weighed into a calibrated 100 ml flask. 60 ml of hot (70 ° C) demineralized water is charged and it is stirred, the temperature at 60 ⁰ C for 15 minutes remains constant. When the solution has cooled, top up to the calibration mark. The resulting solutions are filtered through a membrane filter to a clear solution. From this solution, a volume of 0.1 ml for DHA determination is used.

Measurement conditions:

Cary 300 UV-Vis Spectrophotometer (Varian) (Wavelength = 365 nm, d = 1cm).

As a reference demineralized water is used.

Pitpettenprozedur:

Die Absorption dieser Lösungen ist E1 (Messung 5 Minuten nach Mischung)

The absorption of these solutions is E1 (measurement 5 minutes after mixing)

The solutions are mixed and measured as described above before the enzyme is added. For each sample, the absorbance before enzyme addition is E1.

Subsequent addition of the glycerol dehydrogenase solution in each case 0.01 ml. The absorption of these solutions is E2 (measurement after 15 minutes after addition of the enzyme solution).

ΔE = E1-E2

V = total volume: 3.11 ml v = sample volume: 0.1 ml ε = ε (NADH Na ₂ ) = 3.42 l ^* mmol ^{"1 *} cm ^{" 1}

MW = molecular weight (DHA): 90.08 g / mol EW = sample solution concentration (g / L)

Content of DHA [wt% in test formulation] logo CNRS logo INIST

ΔE ^* V ^* MW ^* 100 ε ^* d ^* v ^* 1000 ^* EW (g / L)

With this described enzyme-based method, degradation is determined in the following test formulations using the test formulation described in Example 3a, abbreviated Eusolex T-VP 0608/08, and 3b, abbreviated Eusolex T-VP 0608/10.

RT = room temperature

Formulation Example 1: Sunscreen Soft Cream (O / W)

Raw material (INCI)% by weight

A

Product from Example 2a 3.00

Steareth-10, steareth-7, stearyl alcohol 2.00

Glyceryl stearate, ceteth-20 2.00

Glyceryl stearate 3.00

Microwax 1, 00

Oleyl oleates 6.00

Cetearyl octanoate 14.00

Caprylic / capric triglyceride 4.00

Propylparaben 0.05

B

Propylene glycol 4.00

Allantoin 0.20

Water 60.60

Methylparaben 0.15

production:

Heat Phase A and Phase B to 80 ^° C. Slowly add phase B to phase A while stirring, homogenize and cool with stirring.

Formulation Example 2: Sunscreen Soft Cream (O / W)

Commodity (INCI)%

A

Product from Example 2b 10.00

Steareth-10, steareth-7, stearyl alcohol 3.00

Glyceryl stearate, ceteth-20 3.00

Glyceryl stearate 3.00

Microwax 1, 00

Oleyl oleates 4.00

Cetearyl octanoate 10.50

Caprylic / capric triglyceride 4.00 Propylparaben 0.05 B

Propylene glycol 4.00

Allantoin 0.20

Water 57,10

Methylparaben 0.15

production:

Heat phase A and B to 80 ^° C. Slowly add phase B to phase A with stirring, homogenize and cool while stirring.

Formulation Example 3: Sunscreen Lotion (O / W)

Commodity (INCI)%

A

Octocrylene 6.00

Butyl methoxydibenzoylmethane 2.00

Polyglyceryl-3 methylglucose distearate 4.00

Ethylhexyl stearate 8.00

Cetearyl isononanoate 2.00

PVP / eicosene copolymer 1, 00

Tocopheryl acetate 1, 00

B

Xanthan gum 0.30

Sodium cetearyl sulfate 1, 00

Glycerin 5.00

Water 65.70

C

Product from Example 2a 4.00

D

Phenoxyethanol, butylparaben, ethylparaben, propylparaben, methylparaben 1, 00 production:

Heat phase A to 80 ^° C. The Keltrol the phase B pre-soak in the water, then add the remaining raw materials and heating to 80 ⁰ C. Homogenize phase A to phase B and homogenize for 2 minutes (hand blender): cool with stirring and add phase C at 35 ^° C. Homogenize again for 1 min (hand blender). Cool to room temperature and stir in phase D.

Formulation Example 4: Sunscreen Lotion (O / W)

A

Steareth-10, steareth-7, stearyl alcohol 3.00

Glyceryl stearate, ceteth-20 3.00

Cetearyl octanoate 13.00

Glyceryl stearate 3.00

Oleyl oleates 7,00

Microwax 1, 00

Caprylic / capric triglyceride 6.00

Preservatives q.s.

Butyl methoxydibenzoylmethane 2.00

B

33% aqueous dispersion of the product

Example 2a 16.70

Propylene glycol 4.00

Allantoin 0.20

Water ad 100

Preservatives q.s.

C

Water 10.00

Dihydroxyacetone 4.00

production:

Heat phase A to 75 ^° C. and phase B to 80 ^° C. Slowly stir phase B into phase A. Homogenize and cool while stirring. Formulation Example 5: Sunscreen Spray Lotion (O / W)

A

Product from Example 2b 5.00

Ethylhexyl methoxycinnamate, BHT 7.50

Benzophenone-3 2.50

PEG-100 stearate, glyceryl stearate 2.80

PPG-1-PEG-9 lauryl glycol ether 0.40

Dicapryl ether 4.50

Steareth-10 0.50

Stearyl alcohol 0.60

Dimethicone 2.00

B

Dimethicone copolyol phosphate 2.50

Chitosan glycolate 2.00

Glycerol 2.50

Water ad 100

C

PPG-1 trideceth-6, polyquaternium-37, propylene glycol dicaprylate / dicaprate 0.40

D

Preservatives q.s.

Water demineralized 10.00

Dihydroxyacetone 3.00

production:

Add phase A except for the titanium dioxide and heat to 60 ⁰ C. Slowly incorporate titanium dioxide into the molten oil phase. Disperse Phase B-1 heat to 60 ⁰ C, then phase B-2 with stirring. Stir phase A into phase B under high energy input. Cool with stirring and at 40 ^° C., add phase C. Homogenize and add while stirring D phase. Formulation example 6

In the following, exemplary formulations for cosmetic preparations are given, which are obtained in the same way with titanium dioxide according to Example 2a or 2b (in the table jewels referred to as titanium dioxide). Otherwise, the INCI names of the commercial compounds are given.

UV-Pearl, OMC stands for the preparation with the INCI name:

Water (for EU: Aqua), Ethylhexyl Methoxycinnamate, Silica, PVP, Chlorphenesin,

BHT; This preparation is commercially available under the name Eusolex®UV

Pearl ™ OMC available from Merck KGaA, Darmstadt.

The other UV pearls listed in the tables are each assembled analogously, with OMC being replaced by the specified UV filters.

TABLE 1 W / O emulsions (numbers in% by weight)

Tabelle 1 (Fortsetzung)

Table 1 (continued)

Tabelle 1 (Fortsetzung)

Table 1 (continued)

Table 2: O / W emulsions, figures in% by weight

Tabelle 2 (Fortsetzung)

Table 2 (continued)

Tabelle 2 (Fortsetzung)

Table 2 (continued)

Table 3: Gels, numbers in wt%

Tabelle 3 (Fortsetzung)

Table 3 (continued)

Tabelle 3 (Fortsetzung)

Table 3 (continued)

Rezepturbeispiel 7: Sonnenschutzspray mit Bräunungsintensivierung

Formulation example 7: Sunscreen spray with tanning intensification

A) CERALUTION® C; Fa. Sasol 15.0%

B) Product according to Example 2a 5 .0%

Ethylhexyl Methoxycinnamate 4.8% Ethylhexyl Salicylate 4.8% Tocopheryl Acetate 0.6% Cyclomethicone 1.0% C12-15 Alkyl Benzoate 2.5% Tridecyl Salicylate 2.5%

C) Dihydroxyacetone 3% Water (Aqua), Deionized ad 100

Water (Aqua), Deionized with 4% Avicel CL 611 25. 0% (Microcrystalline Cellulose (and) Cellulose Gum)

D) Preservative q.s.

Preparation: Phase B is slowly added to Phase A with stirring at room temperature. Thereafter, Phase C is added. Subsequently, the phase D is added.

INCI CERALUTION® C:

Aqua (and) Capric / Caprylic triglycerides (and) Glycerol (and) Ceteareth-25 (and) Sodium Dicocoylethylenediamine PEG-15 Sulfates (and) Sodium Lauroyl Lactylate (and) Behenyl Alcohol (and) Glyceryl Stearate (and) Glyceryl Stearate Citrate (and) and) Gum Arabic (and) Xanthan Gum (and) Phenoxyethanol (and) Methylparaben (and) Ethylparaben (and) Butylparaben (and) Isobutylparaben

Formulation Example 8: Sunscreen Lotion (O / W);

% Stearyl Alcohol (and) Steareth-7 3.00 (and) Steareth-IO

Glyceryl Stearate (and) Ceteth-20 3.00

Cetearyl Octanoate 15.50

Glyceryl Stearate 3.00

Oleyl Oleate 7,00

Microwax 1, 00

Caprylic / Capric Triglyceride 6,00

B

Product according to Example 2b 5.00

Propylene glycol 4.00

Preservative q. s. Water, demineralized ad 100,00

production:

Stir in titanium dioxide in phase B and heat to 80 ⁰ C. Heat phase A to 75 ^° C. Slowly add phase B to phase A while stirring, homogenize and cool with stirring.

Recipe Example 9: Self Tanning Lotion (W / O)

Raw material INCI [%]

A titanium dioxide 3.00 according to the invention

Abil EM 97 (1) BIS-PEG / PPG-14/14 DIMETHICONE, 1, 50

Cyclopentasiloxane

Abil EM 90 (1) CETYL PEG / PPG-10/1 DIMETHICONE 1, 30

Mirasil CM 5 (2) CYCLOMETHICONE 13,00

Ceraphyl 368 (3) ETHYLHEXYL PALMITATE 2.00

SFE 839 (4) CYCLOPENTASILOXANE, 7,00

DIMETHICONEΛ / INYLDIMETHICONE

CROSSPOLYMER

Tegosoft DEC (1) DIETHYLHEXYL CARBONATE 5.00

Perfume oil Babylon (5) PERFUME 0,30

B Water, demineralized AQUA (WATER) ad 100

DHA (6) DIHYDROXYACETONE 5.00

1, 2-Propanediol (6) PROPYLENE GLYCOL 31, 50

Glycerol, anhydrous (6) GLYCERIN 3.00

Magnesium sulfate heptahydrate (6) MAGNESIUM SULFATE 2.00

Ethanol 96% pure (6) ALCOHOL 8.00

Preservatives q.s.

production:

Homogeneously disperse the TΪO2 in phase A.

Dissolve the magnesium sulfate heptahydrate in the water of phase B, weigh the remaining raw materials and mix. Add phase B slowly in phase A with stirring (with the MFR stirrer at 300-400 rpm) then again for 2 min. stir at 1200 rpm. Homogenize (with the MFR stirrer for 2 min at 2000 rpm).

Sources:

(1) Degussa-Goldschmidt AG (2) Rhodia GmbH (3) ISP Global Technologies (4) GE Silicones Holland (5) Drom (6) Merck KGaA / Rona® (7) Nipa Laboratories GmbH

Formulation example 10: Day cream with DHA Rapid + UV filter (O / W)

Ingredients INCI

Inventive TiO2 4.00

Eusolex OCR (5) OCTOCRYLENE 3.00

Eusolex 9020 (5) BUTYL METHOXYDIBENZOYLMETHANE 1.50

Tego Care 150 (1) GLYCERYL STEARATE, STEARETH-25, CETETH-20, 8.00

STEARYL ALCOHOL

Lanette O (2) CETEARYL ALCOHOL 1.50

Tegosoft liquid (1) CETEARYL ETHYLHEXANOATE 5.00

Miglyol 812 N (3) CAPRYLIC / CAPRIC TRIGLYCERIDE 5.00

Abil-Wax 2434 (1) STEAROXY DIMETICONE 1.20

Dow Corning 200 (100cs) (4) DIMETICONE 0.50

RonaCare® AP (5) BIS-ETHYLHEXYL HYDROXYDIMETHOXY 0.50

BENZYLMALONATE

Preservatives q.s.

B

1, 2-Propanediol (5) PROPYLENE GLYCOL 3.00

Preservatives q.s.

Water, demineralized AQUA (WATER) ad 100 C

DHA Rapid (5) DIHYDROXYACETONE, TROXERUTINE 5.00

Water, demineralized AQUA (WATER) 10.00

(6) PERFUME q.s.

Procedure:

Heat Phase A and Phase B to 80 ^° C. Slowly stir phase B into phase A.

Homogenize.

Cool with stirring. Add phase C at 40 ^° C.

suppliers:

(1) Degussa Goldschmidt AG

(2) Cognis GmbH

(3) Sasol Germany GmbH

(4) Dow Corning

(5) Merck KGaA / Rona®

(6) Bell Flavors & Fragrances

Recipe example 11: Self-tanning care with UV protection (O / W)

Ingredients INCI

Inventive TΪO2 1.50

Imwitor 900 (1) GLYCERYL STEARATE 4.00

Stearic acid (2) STEARiC ACiD 1 .50

Cetyl alcohol (2) CETYL ALCOHOL 1 .50

Arlamol S 7 (3) CYCLOMETHICONE, PPG-15 STEARYL ETHER 0.50

Lanol 99 (4) ISONONYL ISONONANOATE 1 1 .00

Dow Corning 200 (100cs) (5) DiMETHicoNE 2.00

RonaCare ^® tocopherol acetate (2) Tocopheryl Acetate 12:50

Simulgel EG (6) SODIUM ACRYLATE, SODIUM ACRYOYLDIMETHYL 1 .00 TAURATE COPOLYMER, ISOHEXADECANE, POLYSORBATE 80

B

Rhodicare XC (7) XANTHAN GUM 0.30 Glycerol, anhydrous (2) GLYCERIN 1.00 Water, demineralized AQUA (WATER) ad 100

C Dihydroxyacetone (2) DIHYDROXYACETONE 3.00 Preservative q.s.

Water, demineralized AQUA (WATER) 20.00

D Eusolex UV-Pearls ™ OMC (2) AQUA (WATER), ETHYLHEXYL METHOXYCINNAMATE.13.80

SLICCA, PVP, CHLOROPHENESINE. BHT

production:

Heat phases A and B separately to 75 ° C. Phase B while stirring in

Enter phase A.

Cool with stirring and at 30 ° C successively incorporating the phases C and D.

Adjust the pH to 4 - 4.5 with citric acid.

Manufacturer:

(1) Sasol Germany GmbH (2) Merck KGaA / Rona® (3) Uniqema

(4) Seppic (5) Dow Corning (6) Gattefosse GmbH

(7) Rhodia GmbH (8) Nipa Laboratories GmbH

Formulation Example 12: Self-Tanning Gel Emulsion (W / Si)

Raw material INCI [%]

Dow Corning 5225C (1) CYCLOPENTASILOXANE. PEG / PPG-18/18 20.00

DIMETHICONE

DM-Fluid-A-6cs (2) DIMETHICONE 4.00

Soya oil (3) GLYCINE SOY (SOYBEAN OIL) 2.00

RonaCare ^® tocopherol acetate (4) Tocopheryl Acetate 0.50

B Inventive TiO ₂ (Ex. 2) 2.50 RonaCare ^® ectoine (4) ECTOIN 0.30

1, 2-propanediol (4) PROPYLENE GLYCOL 30,00

Dipropylene glycol (5) DIPROPYLENE GLYCOL 10.00

Sodium chloride (4) SODIUM CHLORIDE 1, 00

Ethanol 96% pure (4) ALCOHOL 5.00

1% Caramel 250 in water (6) CARAMEL 2.50

1% FD & C Yellow No. 6 in water (5) AQUA (WATER), Cl 15985 (FD & C YELLOW NO 6) 0.25

Water, demineralized AQUA (WATER) ad 100

C

Dihydroxyacetone (4) DIHYDROXYACETONE 3.50

Water, demineralized AQUA (WATER) 10.00

D Perfume (7) PERFUME q.s.

production:

Slowly add the dissolved phase B to phase A with stirring (at about 400 rpm with the MFR stirrer).

Then add phase C and phase D. Then stir for approx. 1 min. At 900 rpm. Homogenize (1 min at 2000 rpm with the MFR stirrer)

Sources:

(1) Dow Corning (2) S. Black GmbH (3) Gustav Heess GmbH

(4) Merck KGaA / Rona® (5) BASF AG

(7) drom

Recipe Example 13: Light & Sparkling For Tanning Cream (O / W)

Ingredients INCI [%]

Inventive TiO ₂ (Ex. 2b) 1, 50

Montanov 68 (1) CETEARYL ALCOHOL, CETEARYL GLUCOSIDE 4.00

Lanette O (2) CETEARYL ALCOHOL 1 .00

Span 60 (3) SORBITAN STEARATE 1 .50

Cosmacol ELI (4) C12-13 ALKYL LACTATE 4.00

Cosmacol EMI (4) Dl-C 12-13 ALKYL MALATE 2.50

Arlamol HD (3) isoHEXADECANE 3.00

RonaCare ^® Tocopherol Acetate (5) TOCOPHERYL ACETATE 0.50

B

Ronastar Silver (5) CALCIUM ALUMINUM BOROSILICATE, SILICA, 1.00

Cl 77891 (TITANIUM DIOXIDE), TIN OXIDE

RonaCare ^® Ectoin (5) ECTOIN 0.50

Glycerol, anhydrous (5) GLYCERIN 3.00

Preservatives q.s.

Water, demineralized AQUA (WATER) ad 100

C

Sepigel 305 (1) LAURETH-7, POLYACRYLAMIDE, C13-14 ISOPARAFFIN 0.60

D

DHA Plus (5) DIHYDROXYACETONE, SODIUM METABISULFITE, 2.00

MAGNESIUM STEARATE

Water, demineralized AQUA (WATER) 4.00

E Perfume (7) PERFUME q.s.

production:

Heat phase A and B separately to 75 ° C. Add phase A to phase B with stirring. At 50 ^° C., add phase C to phase A / B and homogenize. At 4O ⁰ C, add phases D and E in succession, cool to RT while stirring.

Suppliers:

(1) Seppic (2) Cognis GmbH (3) Uniqema

(4) Nordmann & Rassmann (5) Merck KGaA / Rona ^ (6) Nipa Laboratories GmbH

(7) drom Formulation example 14: Self-tanning lotion (O / W) (spray or impregnation solution for wipes)

Ingredients INCI [%]

A

Inventive TiO ₂ 1.00

Prisorine 2021 (2) ISOPROPYL ISOSTEARATE 8.00

Prisorins 2034 (2) PROPYLENE GLYCOL ISOSTEARATE 1.00

Arlasolve 200 (2) ISOCETETH-20 3.78

Arlacel 987 (1) SORBITAN ISOSTEARATE 1.12

Atlas G-2330 (1) SORBETH-30 1.50

B dihydroxyacetone (3) DIHYDROXYACETONE 5.00

Water, demineralized AQUA (WATER) ad 100

Arlasolve DMI (1) DIMETHYL ISOSORBIDE 3.00

C

Preservatives q.s.

1, 2-propanediol (3) PROPYLENE GLYCOL 0.56

D

Perfume (4) PERFUME q.s.

production:

Mix phase A until everything is homogeneous. Mix phase B until a transparent one

Solution is obtained.

Add phase A to phase B with stirring. Homogenize. Adjust pH to approx. 4.

Add phase C & D with stirring.

Suppliers:

(1) Uniqema (2) Uniqema Chemie GmbH (3) Merck KGaA / Rona® (4) Parfex (5) ISP Global Technologies

Formulation Example 15: Day Care Cream DUO-ACTIV (O / W) Raw Material INCI [%]

(1) TiO ₂ 2.00 according to the invention

Eusolex® 9020 (1) BUTYL METHOXYDIBENZOYL METHANE 2.00 Eusolex® OCR (1) OCTOCRYLENE 1.00 Arlacel 165 VP (2) GLYCERYL STEARATE, PEG-100 STEARATE 1 0.00 Cetyl Alcohol (1) CETYL ALCOHOL 2.00 Cetiol B ( 3) DIBUTYL ADIPATE 1 5.00 Paraffin liquid (D PARAFFINUM LIQUIDUM (MINERAL OIL) 9,00

Shea butter firm (4) BUTYROSPERMUM PARKII (SHEA BUTTER) 2.00

Dow Corning 200 Fluid (350 es) (5) DIMETHICONE 0.50

Antioxidant q.s.

Preservatives q.s.

B

RonaCare® Ectoin (1) ECTOIN 0.30 Karion FP, liquid (1) SORBITOL 3.00 Glycerin, anhydrous (1) GLYCERIN 2.00

Complexing agent q.s.

Preservatives q.s.

Water, demineralized AQUA (WATER) ad 100

Dihydroxyacetone (1) DIHYDROXYACETONE 3.00

Erythrulose (6) ERYTHRULOSIS 1, 50

Water, demineralized AQUA (WATER) 10.00

production:

Heat phase A to 75 ° C, phase B to 80 ° C. Slowly stir phase B into phase A.

Homogenize and cool while stirring. Stir at 40 ^° C. phase C.

Sources:

(1) Merck KGaA / Rona®

(2) Uniqema

(3) Cognis GmbH

(4) H. Erhard Wagner GmbH

(5) Dow Corning

(6) PENTAPHARM / DSM

Formulation example 16: sun protection cream high protection (O / W)

Ingredients INCI [%]

A

33% oily dispersion of the TiO ₂ according to the invention 13.00

Eusolex ^® OCR (1) OCTOCRYLENEI O.OO

Eusolex ^® 9020 (1) Butyl Methoxydibenzoylmethane 4:00

Eusolex ^® 4360 (1) BENZOPHENONE-3 4.00

Emulgade F (2) SODIUM CETEARYL SULFATE, CETEARYL ALCOHOL, 3.00

PEG-40 CASTOR OIL

Tegin (3) GLYCERYL STEARATE SE 1.50

Syncrowax HGLC (4) C18-36 ACID TRIGLYCERIDE 1.50

Softisan 100 (5) HYDROGENATED COCO-GLYCERIDES 1.50

Dow Corning 345 (6) CYCLOMETHICONE 6.00 X-Tend 226 (7) PHENYLETHYL BENZOATE 4.50

Antaron V-216 (7) PVP / HEXADECENE COPOLYMER 1.00

Oxynex ST Liquid (1) DIETHYLHEXYL SYRINGYLIDENEMALONATE 0.50

Preservatives q.s.

B Eusolex ^® 232 (1) Phenylbenzimidazole Sulfonic Acid 3:00

Triethanolamine (1) TRIETHANOLAMINE 1.60

Keltrol RD (9) XANTHAN GUMO.20

RonaCare ^® Ectoin (1) ECTOIN 0.10

Glycerol, anhydrous (1) GLYCERIN 5.00

Complexing agent q.s.

Preservatives q.s.

Water, demineralized AQUA (WATER) ad 100

Perfume PERFUME q.s.

Put Eusolex 232 in water and disperse good. Neutralize with triethanolamine until a clear solution is obtained.

Stir Keltrol into Phase B water while stirring until homogeneous

"Gel" is present, then add with stirring the remaining ingredients of phase B and stir at room temperature until a homogeneous phaser is present. phase

Mix A and stir briefly at RT.

Heat phase A and B separately to 80 ^° C., add phase A with stirring to phase B and homogenize.

Cool to RT with stirring (check the pH should be pH 7). Add perfume under stirring.

suppliers:

(1) Merck KGaA / Rona® (2) Cognis GmbH (3) Degussa-Goldschmidt AG

(4) Croda GmbH (5) Sasol Germany GmbH (6) Dow Corning

(7) ISP Global Technologies (8) BASF AG (9) C.P. Kelco

Claims

Patent claims 1. Hydrothermally treated titanium dioxide particles, post-treated with a silicon dioxide coating, the SiO ₂ content in the coating being 25 to 45 percent by weight, based on the TiO ₂ content of the particles to be coated. 2. Titanium dioxide particles according to claim 1, wherein in addition to the SiO ₂ coating, a further coating is applied, containing organic acids selected from the group of stearic acid, lauric acid, caproic acid or palmitic acid, polyols or organosilicon compounds. 3. Titanium dioxide particles according to claim 1 or 2, characterized in that the titanium dioxide is doped with iron. 4. Titanium dioxide particles according to one or more of claims 2 to 3, characterized in that the organosilicone compound is selected from silicone oils or alkylsilanes. 5. Preparation containing titanium dioxide particles according to one of claims 1 to 4. 6. Preparation according to claim 5, characterized in that it is an aqueous or oily dispersion. 7. Preparation according to claim 5, characterized in that it is a topically applicable preparation. 8. Preparation according to claim 5, characterized in that it is a preparation selected from the group of fibers, textiles, including their coatings, paints, Coating systems, films and packaging for the protection of food, plants or technical goods. 9. Preparation according to claim 5, 6 or 7, characterized in that the preparation contains dihydroxyacetone or a dihydroxyacetone derivative. 10. Preparation according to claim 9, characterized in that Concentration of dihydroxyaxetone or the dihydroxyacetone derivative is in the range from 1 to 12 percent by weight, based on the preparation. 11. Preparation according to one or more of claims 5 to 10, characterized in that the preparation contains at least one organic UV filter 12. Preparation according to one or more of claims 5 to 11, characterized in that the preparation contains one or more antioxidants. 13. Process for producing a preparation according to one or more of the Claims 7 and 9 to 12, characterized in that titanium dioxide particles according to at least one of claims 1 to 4 are mixed with a cosmetically or dermatologically suitable carrier and optionally other ingredients. 14. Use of the titanium dioxide particles according to one or more of the Claims 1 to 4 for stabilizing dihydroxyacetone or derivatives of dihydroxyacetone.